CN107002272A

CN107002272A - Mould, the manufacture method of mould, the manufacture method of antireflection film and antireflection film

Info

Publication number: CN107002272A
Application number: CN201580060462.5A
Authority: CN
Inventors: 山田美穗; 箕浦洁; 中原隆裕
Original assignee: Sharp Corp
Current assignee: Sharp Corp
Priority date: 2014-11-21
Filing date: 2015-11-13
Publication date: 2017-08-01
Anticipated expiration: 2035-11-13
Also published as: CN107002272B; WO2016080314A1; JP6322294B2; JPWO2016080314A1

Abstract

The manufacture method of mould (100), comprising with the cylindric aluminium base (12) of the aluminium alloys of Al Mg Si systems formation and be applied in mechanicalness mirror finish aluminium base (12) process, the process that the surface of aluminium base (12) leads to peralkaline etching solution satin weave processing, inorganic material layer (16) is formed with thereafter by the surface of aluminium base (12), process of the aluminium film (18) to make mould base material (10) is formed on inorganic material layer (16), and be directed to mould base material (10) aluminium film (18) be alternately repeated anodic oxidation with etching, form the process by reversion moth eye construction with multiple nick portions (14p).

Description

Mould, the manufacture method of mould, the manufacture method of antireflection film and antireflection film

Technical field

The present invention is on mould, the manufacture method of mould, utilizes the antireflection film and antireflection film manufactured by mould Manufacture method.Herein described " mould ", comprising mould used in various processing methods (punching press or casting), also referred to as press Mould.In addition, may be alternatively used for printing (including nano print).

Background technology

For using in the optical element of the display device or camera lens of TV or portable phone etc. etc., generally Apply antireflection technique to reduce surface reflection and improve the transmission amount of light.For example, such as share the same light incident air and glass During interface, when light is by the interface of the different medium of refractive index, the transmission amount of light lowers because of Fresnel reflection etc., and causing can Depending on property reduction.

In recent years, as antireflection technique, by concavo-convex periodic Control visible light (λ=380nm~780nm) wavelength Following miniature relief pattern formation persistently attracts attention (with reference to patent document 1 to 3) in the method for substrate surface.Constitute performance The two-dimensional of the convex portion of the relief pattern of anti-reflective function is in more than 10nm, less than 500nm.Here, " the two-dimentional chi of convex portion It is very little " when referring in terms of normal to a surface direction, the area circle equivalent footpath of convex portion, such as when cone is in convex portion, convex portion Two-dimensional be comparable to the diameter of circular cone bottom surface." two-dimensional " of recess is same.

This method, that is, using the principle of moth eye (Moth-eye, the eye of moth) structure, by relative to incident substrate The refractive index of light continuously changes to the refractive index of substrate from the refractive index of incident medium, thus along concavo-convex depth direction To suppress the reflection for being intended to prevent the wavelength band of reflection.

The structure of moth eye, in addition to it can play in the small antireflection effect of the incident angle dependency for covering wide wavelength band, Also have the advantages that being applied to many materials, relief pattern can directly form on substrate.As a result, can provide low cost and High performance antireflection film (or antireflective surfaces).

Present invention applicant, as the manufacture method of the antireflection film (or antireflective surfaces) with moth ocular structure, opens The method (patent document 2 and 3) of the anodic oxidation porous alumina layer obtained with aluminium by anodic oxidation is sent out.

By using anodic oxidation porous alumina layer, the mould moth ocular structure to be formed to surface can be easily manufactured Have (hereinafter referred to as " the ophthalmically acceptable mould of moth ").Particularly, as described in patent document 2 and 3, if directly utilizing the anodic oxygen of aluminium Change the surface of film as mould, then the effect for lowering manufacturing cost is very big.The surface of the ophthalmically acceptable mould of moth of moth ocular structure can be formed Structure, be referred to as " by reversion moth ocular structure ".

In addition, as described in patent document 1 to 4, in addition to moth ocular structure (micro-structural), by setting than moth ocular structure Bigger concaveconvex structure (macrostructure), can assign anti-glare (anti-dazzle) function in antireflection film (antireflective surfaces).Constitute and play The convex portion of concaveconvex structure (situation for also having referred to as " anti-glare structure ") of anti-glare function or the two-dimensional of recess exist More than 200nm, less than 100 μm.In addition, the structure on the surface of the mould of anti-glare structure can be formed, it is also referred to as " anti-dizzy by reversion Photo structure ".The disclosure of patent document 1 to 4 is all incorporated in this specification to refer to.

And, in this manual, constituting the bumps of moth ocular structure (or for by reversion moth ocular structure), to be referred to as nick convex, The bumps for constituting anti-glare structure (or for by reversion anti-glare structure) are referred to as grand bumps.The model of grand concavo-convex two-dimensional Enclose, the scope of convex two-dimensional overlaps with nick, in the antireflection film (antireflective surfaces) with anti-glare function In, the concaveconvex structure of anti-glare structure is constituted, it is bigger than constituting the concaveconvex structure of moth ocular structure of performance anti-reflective function.

Patent document 1：Japanese Unexamined Patent Application Publication 2001-517319 publications

Patent document 2：Japanese Unexamined Patent Application Publication 2003-531962 publications

Patent document 3：International Publication 2011/055757

Patent document 4：International Publication 2013/146656

The content of the invention

However, efficiently manufacturing to form the antireflection film (or antireflective surfaces) of the anti-glare function with appropriateness The method of mould be hardly established.

For example, the sand-blast recorded in patent document 1, it is difficult to which repeatability forms the institute's phase for assigning anti-glare function well The grand concaveconvex structure hoped.In addition, the katholysis recorded in patent document 3, anti-glare can be given full play to by having to be formed The situation of the grand concaveconvex structure of function.

In addition, the resin bed by electroplating formation that reflection is recorded for patent document 4 is continuous grand without flat part The surface of concaveconvex structure, the problem of having image blurring.In recent years, with display device High precision progress, with suppression The antireflection film of imaged fuzzy appropriate anti-glare function is persistently pursued.

It is an object of the invention to provide the antireflection film of the anti-glare function with appropriateness and the specular reflective of appropriateness (or antireflective surfaces), the manufacture method of above-mentioned antireflection film, the mould to form above-mentioned antireflection film and can be well to imitate The method that rate manufactures above-mentioned mould.

The manufacture method of the mould of embodiment of the present invention, prepares to form circle with the aluminium alloy of Al-Mg-Si systems comprising (a) Tubular and be applied in mechanicalness mirror finish aluminium base process, (b) is by the surface of the aluminium base by containing hydrogen fluoride The process handled with the aqueous solution satin weave of the salt of ammonia, (c) after the process (b), by described in the aluminium base Surface forms inorganic material layer, aluminium film is formed on the inorganic material layer with the process for making mould base material, (d) is in described After process (c), by making the surface anodization of the aluminium film, the work of the porous alumina layer with multiple nick portions is formed Sequence, (e) by making the porous alumina layer contact etching solution, expands the porous alumina layer after the process (d) The multiple nick portion process, and (f) is after the process (e), by further anodic oxidation, makes the multiple The process of nick portion growth.

In certain embodiment, the aluminium base is to apply the aluminium base after cold-drawn processing.The aluminium base is by heat The aluminium base that extrusion is formed.Hot extrusion method can be heart method of principal axes or duct method.Cold-drawn processing can be omitted. Situation about being processed without cold-drawn, it is preferable to use the aluminium base being formed with heart method of principal axes.

In certain embodiment, the manufacture method of the mould also comprising degreasing process and is washed before the process (b) Wash process.

In certain embodiment, the process (b) is carried out after the washing procedure before expiring within 15 minutes.

In certain embodiment, the manufacture method of the mould also includes the erosion using alkalescence before the process (b) Liquid is carved, the substrate surface etching work procedure that the surface of the aluminium base is etched.

In certain embodiment, the substrate surface etching work procedure doubles as the degreasing process.

In certain embodiment, the alkaline etching solution contains more than 0.03mass% inorganic alkali or organic salt Base.

In certain embodiment, the pH value of the alkaline etching solution is more than 10 and less than 12.

In certain embodiment, the alkaline etching solution contains potassium hydroxide.

In certain embodiment, the alkaline etching solution contains the organic compound with amido.

In certain embodiment, by the substrate surface etching work procedure and the process (b), the aluminium base it is described The arithmetic average roughness Ra on surface is more than 50nm and below 300nm.

In certain embodiment, among the substrate surface etching work procedure, removed at least from the surface of the aluminium base 1.4μm。

In certain embodiment, before the process (b), also comprising to the anodic oxidation process of preposition processing and erosion Carve process.

In certain embodiment, to the anodic oxidation process of preposition processing, electrolysis is used as using aqueous sulfuric acid Liquid.

In certain embodiment, to the etching work procedure of preposition processing, etching solution is used as using phosphate aqueous solution.

In certain embodiment, the hydrogen fluoride of the process (b) and the salt of ammonia are ammonium acid fluorides.In certain embodiment party Among formula, the aqueous solution of the salt containing hydrogen fluoride and ammonia, the ammonium acid fluoride containing more than 4mass%.The process (b), example Such as with about 10 DEG C of progress.Now, the time of satin weave processing is preferably the scope of 2 points of more than 30 seconds and less than 8 points.

The mould of embodiment of the present invention, is the mould manufactured by the manufacture method of the mould of any of the above-described record.

The mould of others embodiment of the invention, with the porous alumina layer for possessing surface structure, the surface structure Make with terms of normal to a surface direction when two-dimensional for less than more than 200nm and 30 μm multiple grand convex portions and Two-dimensional when in terms of normal to a surface direction is for more than 10nm and less than 500nm multiple nick portions.

The manufacture method of the antireflection film of embodiment of the present invention form, the process comprising the above-mentioned any mould of preparation, Prepare machined object process, between the surface of the mould and the machined object assign light-hardening resin in the state of, By to the light-hardening resin irradiation light so that process that the light-hardening resin is hardened and by the mould to harden Light-hardening resin formation antireflection film peel off process.

The antireflection film of embodiment of the present invention, is the antireflection manufactured by the manufacture method of above-mentioned antireflection film Film.

The antireflection film of others embodiment of the invention, possesses two dimension when with terms of normal to a surface direction Size is less than more than 200nm and 30 μm of multiple recesses and two-dimensional when in terms of normal to a surface direction is More than 10nm and the surface structure in multiple dimpling portions less than 500nm, if incidence angle is 5 °, take acceptance angle as transverse axis, overflow anti- The maximum of luminous intensity is penetrated as 80% normalized common logarithm for taking relative diffusing reflection rate (%) as the light of the longitudinal axis The inclination of distribution curve is that the point discontinuously changed is present in acceptance angle more than 0 ° in less than 10 ° of scope, and is overflow relatively Reflectivity (%) is in more than 1% and less than 10% scope.

In certain embodiment, the haze value of the antireflection film is about more than 7 and about less than 24.

The manufacture method of the mould of others embodiment of the invention, prepares with the aluminium alloy of Al-Mg-Si systems comprising (a) The process for forming aluminium base that is cylindric and being applied in mechanicalness mirror finish, the surface of the aluminium base is passed through alkalescence by (b) Etching solution satin weave processing process, (c) after the process (b), by the surface of the aluminium base formed nothing Machine material layer, forms process of the aluminium film to make mould base material on the inorganic material layer, (d) in the process (c) it Afterwards, by making the surface anodization of the aluminium film, the process for forming the porous alumina layer with multiple nick portions, (e) in After the process (d), by making the porous alumina layer contact etching solution, expand the described many of the porous alumina layer The process in individual nick portion, and (f) is after the process (e), by further anodic oxidation, make the multiple nick portion into Long process.

In certain embodiment, by the process (b), the arithmetic average roughness Ra on the surface of the aluminium base is More than 50nm and below 200nm.

In certain embodiment, the alkaline etching solution, inorganic alkali or organic alkali containing more than 0.03mass%. For example, the alkaline etching solution, organic alkali containing more than 0.96mass%.

In certain embodiment, the pH value of the alkaline etching solution is more than 9.5 and less than 11.

In certain embodiment, in the process (b), at least 1.4 μm are removed from the surface of the aluminium base.

In certain embodiment state, the process (b) is described alkaline by contacting the surface of the aluminium base Etching solution is carried out for more than 45 minutes.

In certain embodiment, the process (b) doubles as degreasing process.

In certain embodiment, the aluminium base is the aluminium base formed by heart method of principal axes.

The mould of others embodiment state of the invention, is manufactured by the manufacture method of the mould of any of the above-described record Mould.

The manufacture method of the antireflection film of others embodiment of the invention, includes the work for preparing above-mentioned any mould Sequence, prepare machined object process, between the surface of the mould and the machined object assign light-hardening resin state Under, by the light-hardening resin irradiation light so that the light-hardening resin harden process and by the mould from The process that the antireflection film of the light-hardening resin formation of hardening is peeled off.

The antireflection film of others embodiment of the invention, is by preventing that the manufacture method of above-mentioned antireflection film is manufactured Reflectance coating.

According to embodiment of the present invention, it is possible to provide the anti-glare function appropriate to be formed and the specular reflective of appropriateness The mould of antireflection film (or antireflective surfaces), and the method that above-mentioned mould can be manufactured with good efficiencies.By of the invention real The mould of mode is applied, the specular reflective and excellent anti-reflective function for possessing appropriate anti-glare function and appropriateness can be formed Antireflection film (antireflective surfaces).According to the antireflection film of the embodiment of this hair, anti-glare function with performance appropriateness and The surface texture of the specular reflective of appropriateness, excellent anti-reflective function.

Brief description of the drawings

Fig. 1 (a)~(d) is the section of the manufacture method for the ophthalmically acceptable mould 100 of moth for illustrating embodiment of the present invention 1 Schematic diagram, (a) is the diagrammatic cross-section of the aluminium base 12 of the ophthalmically acceptable mould 100 of moth, and (b) is schematically illustrated with by reversion anti-glare The profile of the surface texture of the aluminium base 12 of structure, (c) is to be formed with inorganic material layer 16 and aluminium on the surface of aluminium base 12 The diagrammatic cross-section of the mould base material 10 of film 18, (d) is that have by reversion anti-glare structure, on by reversion anti-glare structure quilt The diagrammatic cross-section of the overlapping ophthalmically acceptable mould 100 of moth by reversion moth ocular structure.

Fig. 2 is the description of flow diagram of the manufacture method of the ophthalmically acceptable mould 100 of moth of embodiment of the present invention 1.

Fig. 3 (a) is the laser with the surface that the aluminium base 12 by reversion anti-glare structure formed is handled by satin weave Microscopic iage (full size is 15 μm in microscopic iage), (b) is that have the quilt formed by satin weave processing from vertical direction SEM pictures (in SEM pictures full size be 10 μm) during the surface for the aluminium base 12 for inverting anti-glare structure, (c) be inverted it is anti-dizzy The floor map of photo structure.(d) it is the schematic perspective view that is inverted anti-glare structure.

SEM pictures (full size in SEM pictures when Fig. 4 A (a) is the surface of the aluminium film 18 of the mould base material 10 from vertical direction For 10 μm), (b) is the porous alumina layer by reversion moth ocular structure with the ophthalmically acceptable mould 100 of moth from vertical direction SEM pictures during surface (full size is 10 μm in SEM pictures).

Fig. 4 B (a) and (b) is that the section of the manufacture method for the ophthalmically acceptable mould 100 of moth for illustrating embodiment of the present invention 2 shows It is intended to, (a) is schematically illustrated with by the profile of the surface texture of the aluminium base 12 of reversion anti-glare structure, and (b) is in aluminium The surface of base material 12 is formed with the diagrammatic cross-section of inorganic material layer 16 and the mould base material 10 of aluminium film 18, and (c) is that have to pass through By the laser capture microdissection on the surface of the aluminium base 12 of reversion anti-glare structure formed by the satin weave processing that the etching solution of alkalescence is carried out Mirror image.

Fig. 5 is the figure for the manufacture method for illustrating the antireflection film using the ophthalmically acceptable mould 100 of moth.

Fig. 6 (a) and (b) is the SEM pictures of the antireflection film with anti-glare function of embodiment of the present invention, and (a) is from vertical Nogata is to the SEM pictures (full size is 10 μm in SEM pictures) during the surface for observing antireflection film, and (b) is the counnter attack from tilted direction SEM pictures when penetrating section and the surface of film (full size is 3 μm in SEM pictures).

Fig. 7 (a)~(c) is the schematic diagram of the antireflection film with anti-glare function of embodiment of the present invention, and (a) is from vertical Nogata is to the schematic diagram during surface for observing antireflection film, schematic diagram when (b) is the surface of antireflection film from tilted direction, (c) be antireflection film diagrammatic cross-section.

Fig. 8 (a) is the measurement result for representing the light diffused the distribution that the antireflection film with anti-glare function is caused Chart, (b) is to represent the measurement system schematic diagram that the light diffused is distributed.

Fig. 9 (a)~(c) is with the SEM pictures (5000 on the surface of the aluminium base containing the progress satin weave processing of the ammonium acid fluoride aqueous solution Times, full size is 10 μm in SEM pictures).

Figure 10 A are the aluminium bases (the mould base material processed by cold-drawn) for representing that the time of satin weave processing (35 DEG C for the treatment of temperature) is different Used as mould, produce the figure of the light diffused the distribution of sample film.

Figure 10 B are the figures for representing anti-glare function and the evaluated the model calculation of specular reflective.

Figure 11 is the aluminium base (the mould base material processed by cold-drawn) for representing that the time of satin weave processing (10 DEG C for the treatment of temperature) is different Used as mould, produce the figure of the light diffused the distribution of sample film.

Figure 12 (a) and (b) is to represent to carry out the aluminium base of the anodic oxidation of the preposition processing and etching handled as satin weave (not The mould base material processed by cold-drawn) surface SEM pictures, (a) is the situation for using oxalic acid aqueous solution as electrolyte, and (b) is The situation of electrolyte is used as using aqueous sulfuric acid.

Figure 13 (a)~(d) is to use the preposition processing handled as satin weave to use aqueous sulfuric acid to carry out after anodic oxidation The SEM pictures on the surface of the different sample of the etching period of phosphate aqueous solution.

Figure 14 is after representing the anodic oxidation (aqueous sulfuric acid) for the preposition processing that progress is handled as satin weave and etching, to carry out satin The aluminium base that the processing time of line processing is different is used as mould, the light distribution map diffused for the film produced.

Figure 15 (a) is, in the aluminium base for the mould base material produced using the aluminium base applied after cold-drawn processing, to carry out 37 seconds The SEM pictures on the surface after satin weave processing, (b) is the aluminium of the mould base material to being produced using the aluminium base for not applying cold-drawn processing Base material, carries out after anodic oxidation (aqueous sulfuric acid) and etching as preposition processing, carries out the surface after satin weave processing in 120 seconds SEM pictures.

Figure 16 (a) and (b) is to schematically illustrate to be formed between the grand concaveconvex structure of existing anti-glare structure and the point of line direction The figure of size relationship away from Px.

Figure 17 (a) is the profile for schematically illustrating to be formed the grand concaveconvex structure of existing anti-glare structure, and (b) is to represent weight The grand concavo-convex diagrammatic cross-section by reversion moth ocular structure is laminated on, (c) is by by the diagrammatic cross-section of reversion moth ocular structure amplification.

Embodiment

Hereinafter, referring to the drawings, the mould of embodiment of the present invention and the manufacture method of mould are illustrated.

First, reference picture 16, illustrate to constitute the grand concaveconvex structure of existing anti-glare structure, the point spacing Px with line direction Size relation.Figure 16 (a) and (b), are that will constitute the grand concaveconvex structure that existing anti-glare is constructed, between the point of line direction The figure that the relation of size away from Px is showed schematically, Figure 16 (a) is to represent grand concaveconvex structure than a situation bigger spacing Px, figure 16 (b) is to represent grand concaveconvex structure than a situation smaller spacing Px.Herein, point refers in typical color liquid crystal display panel Among constitute pixel R, G, B each point.That is, the pixel among color liquid crystal display panel, by be arranged in line direction 3 Individual point (R points, G points and B points) and situation about being configured, the pel spacing of line direction turn into 3 times of the point spacing Px of line direction. Also, the pel spacing of column direction is equal with the point spacing Py of column direction.

Such as Figure 16 (a) and (b) are showed schematically, the surface with the grand concaveconvex structure for constituting existing anti-glare structure 28s, with the surface configuration without flat part and continuous wave.Grand concavo-convex knot with the surface configuration of continuous wave as Structure, with distance between adjacent grand recess average value (it is average it is adjacent between apart from AD_int) or recess two-dimensional AD_p's Feature.Though here, it is conceived to grand recess, if being conceived to grand convex portion also has same feature.

As shown in Figure 16 (a), recess it is average it is adjacent between apart from AD_int(think to be the same as the two-dimensional of recess AD_p), more than point spacing Px (situation that pixel is made up of three points (R, G, B), the pel spacing of line direction of such as line direction For 3 times of a spacing) when, then it can not fully obtain anti-glare function.In order that anti-glare function is given full play to, such as Figure 16 (b) shown in, recess it is average it is adjacent between apart from AD_int(the two-dimensional AD of recess_p) roughly equal mutually, and be preferably to compare a little Spacing is smaller.In addition, the two-dimensional of recess refers to, two-dimensional expansion when in terms of normal to a surface direction, the allusion quotation of recess Type is cone, and shape when in terms of normal to a surface direction is generally circular.Now, two-dimensional is equivalent to diameter of a circle. In addition, if convex portion is formed with sufficiently high density, 2 recesses adjacent each other it is average it is adjacent between apart from AD_int, it is and recessed The two-dimensional AD in portion_pIt is roughly equal.During pel spacing is the relatively low display of resolution, such as display of 100ppi, it is 254μm.Be used in the situation of the antireflection film of this display it is average it is adjacent between apart from AD_int, it is preferably from about 85 μm (254/3) below.

Make moth ocular structure overlapping in the anti-glare structure with the surface 28s without flat part and continuous wave as The manufacture method of antireflection film, for example, being recorded in patent document 4.Reference picture 17, illustrate to be recorded in patent document 4 is used to shape Into the manufacture method of the ophthalmically acceptable mould of moth of the antireflection film with anti-glare function.

Figure 17 (a), is to schematically illustrate to form the diagrammatic cross-section by reversion anti-glare structure of anti-glare structure, figure 17 (b), be represent by inverted in anti-glare structure by it is overlapping by reversion moth ocular structure diagrammatic cross-section, Figure 17 (c), be by Invert the diagrammatic cross-section of moth ocular structure amplification.

As shown in Figure 17 (a), the anti-glare knot with surface 28s without flat part and continuous wave foregoing to be formed Structure has by the surface 18cs of reversion anti-glare structure, is on the outer peripheral face of cylindric metal base, by containing disappearing The plated resin formation insulating barrier of photo etching, forms aluminium film 18c, obtains therefrom on the insulating layer.That is, by the electricity containing delustering agent The surface of the insulating barrier of plated resin formation, with the surface configuration without flat part and continuous wave, is formed on the insulating layer Aluminium film 18c surface 18cs, reflects the shape on the surface of insulating barrier, as with the surface shape without flat part and continuous wave Shape.In addition, because aluminium film 18c surface 18cs shape is constituted by reversion anti-glare structure, aluminium film 18c surface 18cs It is grand it is concavo-convex, be for opposite relation with the surface 28s of composition anti-glare structure grand bumps.

Then, as shown in Figure 17 (b), for by the aluminium film 18c of reversion anti-glare structure surface, passing through anodic oxygen Change and be alternately repeated with etching, form the anodic oxidation porous alumina layer 14c with nick portion 14p.Consequently, it is possible to can With obtain with by reversion anti-glare structure by it is overlapping by reversion moth ocular structure surface the ophthalmically acceptable mould 200 of moth.

Porous alumina layer 14c, such as Figure 17 (c) show schematically that nick portion 14p is by intensive filling.Nick portion 14p is rough To be coniform, it is possible to have stepped sides.Nick portion 14p two-dimensional (opening portion diameter：D_p) it is preferably in 10nm Above less than 500nm, depth (D_depth) in more than 10nm less than 1000nm (1 μm) degree.Additionally, it is preferred that being nick portion 14p's Bottom is sharp (bottommost turns into point).In addition, nick portion 14p is preferably by intensive filling, from porous alumina layer 14c method Line direction see when after, nick portion 14p shape is assumed to be circle, and adjacent circle overlaps each other, be preferably in adjacent nick portion Saddle is formed between 14p.In addition, when forming adjacent as saddle between nick portion 14p coniform substantially As, nick portion 14p two-dimensional D_pBe equal to it is averagely adjacent between apart from AD_int.Therefore, to manufacture antireflection film the ophthalmically acceptable mould of moth it is many Porous aluminum oxide layer 14c, with D_p=D_intIn more than 10nm less than 500nm, preferably D_depthIn more than 10nm less than 1000nm (1 μm) the nick portion 14p of degree is by the intensive construction brokenly arranged.The arrangement in nick portion, and non-required completely random, as long as The degree that the interference and diffraction that light can be made do not occur substantially it is irregular all right.In addition, because nick portion 14p opening portion The circle of shape and non-critical, it is advantageous to be D_pSought by the SEM pictures on surface.Porous alumina layer 14c thickness t_pAbout at 1 μm Below.The above-mentioned explanation by reversion moth ocular structure having on porous alumina layer 14c, for embodiment of the present invention The ophthalmically acceptable mould of moth be also appropriate.

The antireflection film formed using the mould manufactured by the manufacture method of the mould as being recorded in patent document 4, is had Image blurring the problem of (afterwards, reference picture 10B illustrates).The reason is that the mould manufactured by the method for being recorded in patent document 4 Have by reversion anti-glare structure, with than larger AD_intAnd AD_p.Therefore, it is recorded in the manufacturer of patent document 4 Method, it is difficult to form the anti-glare structure for being for example suitably used for the fine display more than 300ppi.

Embodiment there is provided the anti-glare function with tool appropriateness, (for example haze value about exists invention described below About more than 7 and about less than 24) anti-glare structure, with the specular reflective of appropriateness, the moth eye with playing excellent antireflection effect The antireflection film (or antireflective surfaces) of structure.In addition, there is provided to form such antireflection film for embodiment of the present invention Mould, in addition, also provide the method that efficiency manufactures such mould goodly.In addition, the mould for passing through embodiment of the present invention The manufacture method of tool and the mould manufactured, are not limited to those illustrated, are also used to form with small haze value (for example About more than 1 and about less than 5) diffusing reflection performance antireflection film.

(embodiment 1)

First, 1~Fig. 4 of reference picture A, illustrate the manufacture method of the mould of embodiment of the present invention 1 and by such manufacture method The structure of the mould manufactured.

Fig. 1 (a)~(d), is that the manufacture method of the ophthalmically acceptable mould 100 of moth that illustrates embodiment of the present invention 1 is cutd open Face schematic diagram, Fig. 2 is the description of flow diagram of the manufacture method of the ophthalmically acceptable mould 100 of moth of embodiment of the present invention 1.

The manufacture method of the ophthalmically acceptable mould 100 of moth of embodiment of the present invention 1, as shown in Fig. 2 including following process (A) ~(F).

(A) prepare with the cylindric aluminium base of the aluminium alloy formation of Al-Mg-Si systems, that is, to apply the mirror finish of machinery Aluminium base process.

(B) process that the surface of aluminium base is handled by the aqueous solution satin weave containing hydrogen fluoride and the salt of ammonia.

(C) after step (B), by forming inorganic material layer on the surface of aluminium base, aluminium film is formed on inorganic material layer, The process for making mould base material.

(D) after step (C), by by the surface anodization of aluminium film, forming the Woelm Alumina with multiple nick portions The process of layer.

(E) after step (D), by the way that porous alumina layer is contacted into etching solution, multiple nick portions of porous alumina layer are expanded Process.

(F) after step (E), by further anodic oxidation, the process of multiple nick portion growth is made.

Among this specification, mould base material refers to, among the manufacturing process of mould, pair for being anodized and etching As.In addition, aluminium base, referring to can be with the aluminium of the block shape of self-sustained.

Then, (a)~(d) of reference picture 1, Fig. 1 (a), are the diagrammatic cross-sections of the aluminium base 12 of the ophthalmically acceptable mould 100 of moth, Fig. 1 (b), is to have by the diagrammatic cross-section of the surface texture of reversion anti-glare structure aluminium base 12, Fig. 1 (c) is in aluminium base 12 surface is formed with the diagrammatic cross-section of inorganic material layer 16 and the mould base material 10 of aluminium film 18, and Fig. 1 (d) is with anti- Turn anti-glare structure, show with by the section of the overlapping ophthalmically acceptable mould 100 of moth by reversion moth ocular structure of reversion anti-glare structure It is intended to.

Fig. 1 be by a part of enlarged representation of the ophthalmically acceptable mould 100 of moth, the ophthalmically acceptable mould 100 of moth of embodiment of the present invention 1, It is for cylindric (roll).As disclosed in the International Publication No. 2011/105206 of present invention applicant, cylindrical shape is used During the ophthalmically acceptable mould of moth, antireflection film can be manufactured well by roll-to-roll mode efficiency.In order to refer to, International Publication No. 2011/ The whole of the disclosure of No. 105206 is referenced to this specification.

First, as shown in Fig. 1 (a), prepare with the cylindric aluminium base 12 of the aluminium alloy formation of Al-Mg-Si systems, that is, to apply Plus the aluminium base 12 of the mirror finish of machinery.

It is used as the mirror finish of machinery, preferably cutter grinding.On the surface of aluminium base 12, such as when abrasive particle is remained, Among the part that there are abrasive particle, the conduction between aluminium film 18 and aluminium base 12 becomes easy.Beyond abrasive particle, exist irregular Place, local conduction becomes easy between aluminium film 18 and aluminium base 12.Between aluminium film 18 and aluminium base 12 during local conduction, There is the possibility for occurring local cell reaction between impurity and aluminium film 18 in base material 12.

Illustrate as after shown in experimental example, according to the material of aluminium base 12, the effect of chemical satin weave processing afterwards is not Together, in order to obtain foregoing grand concaveconvex structure, use what is be formed with the aluminium alloy (for example, JIS A6063) of Al-Mg-Si systems Aluminium base 12.

It is formed for cylindric aluminium base 12, typical case by hot extrusion method.Hot extrusion method, though intentionally method of principal axes and duct Method, but be preferably to use the aluminium base 12 being formed using heart method of principal axes.The aluminium base 12 of cylindrical shape is formed using duct method Outer peripheral face can form seam (weld bond), and seam can be reflected in the ophthalmically acceptable mould 100 of moth.Therefore, according to the pursuit ophthalmically acceptable mould 100 of moth Precision, it is preferable to use utilize the aluminium base 12 of heart method of principal axes formation.

In addition, for the aluminium base 12 using the formation of duct method, being processed by applying cold-drawn, asking for seam can be solved Topic.Certainly, for the aluminium base 12 using the formation of heart method of principal axes, cold-drawn processing can also be applied.

Then, the surface of aluminium base 12 is handled by using the aqueous solution satin weave containing hydrogen fluoride and the salt of ammonia, such as Fig. 1 (b) shown in, the anti-glare structure inverted in the surface 12s formation of aluminium base 12.Pass through being inverted of being formed of satin weave processing Anti-glare structure, with multiple grand convex portion 12p and multiple grand recess 12g.Grand convex portion 12p is substantially surrounded by grand recess 12g, grand Recess 12g exists as provided the groove of grand convex portion 12p peripheries.

The aqueous solution of salt containing hydrogen fluoride and ammonia, can cause pitting corrosion (spot corrosion).It is used as hydrogen fluoride and the salt of ammonia Class, there is ammonium fluoride (normal salt or neutral salt) and ammonium acid fluoride (hydrogen salt or ackd salt).Salt containing hydrogen fluoride and ammonia it is water-soluble Liquid, compared with the aqueous solution of hydrogen fluoride, has the advantages that to give human body or environment harmful effect is few.It is used as hydrogen fluoride and the salt of ammonia Class, uses the situation of hydrogen fluoride, for example, concentration of ammonium acid fluoride, more than 4mass%., can also in addition to ammonium acid fluoride Add ammonium dihydrogen phosphate and/or ammonium sulfate.Here, comprising following experimental example, as the etching solution aluminium satin weave to be handled, Using in ammonium acid fluoride be added with a small amount of ammonium dihydrogen phosphate and ammonium sulfate person.This etching solution in order to simplify and be referred to as containing The aqueous solution of ammonium acid fluoride.Etching solution so, can use the aqueous precise remover of Japanese JCBChem limited companies Modulation is formed.For example, during 35 DEG C for the treatment of temperature, the time handled by the aqueous solution satin weave containing ammonium acid fluoride, be 15 seconds with Upper 180 second is following.It is weak to the etching power of aluminium compared with the aqueous solution containing ammonium acid fluoride because the aqueous solution containing ammonium fluoride, lead to Suitably adjustment concentration, treatment temperature, time are spent, the effect being equal with the situation using the aqueous solution containing ammonium acid fluoride can be obtained Really.

In addition, before by the aqueous solution satin weave processing containing hydrogen fluoride and the salt of ammonia, if it is necessary, carrying out degreasers Sequence and washing procedure.In addition, satin weave is handled, it is preferably to be carried out before expiring within 15 minutes after washing procedure.In addition, making Between process with different treatment fluids, if it is necessary, preferably being washed.

In addition, having carried out the aluminium base 12 of the mirror finish of cutter grinding to not applying cold-drawn processing and having applied satin weave When processing, have and form the situation of cutting vestige on the surface of aluminium base 12.The cutting trace that the surface of aluminium base 12 is formed Mark, can also be reflected in the aluminium film 18 formed on aluminium base 12.The surface of this specification, not only aluminium base 12, in aluminium base 12 On the vestige caused by grinding that is formed in the aluminium film 18 that is formed, also referred to as " grinding vestige ".

Before satin weave processing, by carrying out anodic oxidation process and etching work procedure to preposition processing, grinding can be made Vestige lowers.That is, once the surface anodic oxidation of aluminium base 12, the anode oxide film of formation is removed by etching, can be made Grinding vestige lowers.This is used to the anodic oxidation process of preposition processing, it is preferable to use aqueous sulfuric acid is used as electrolyte With the etching work procedure of preposition processing, it is preferable to use phosphate aqueous solution is used as etching solution.Certainly, it is laggard on applying cold-drawn processing The aluminium base 12 of the mirror finish of row cutter grinding, by carrying out anodic oxidation process and etching work procedure to preposition processing, The situation for producing grinding vestige on the surface of aluminium base 12 can more reliably suppress.

In addition, foregoing grinding vestige is regarded as, the mirror finish carried out by cutter grinding, due to aluminium base 12 Surface formed affected layer etching it is uneven.Therefore, the problem of cutting vestige is such is formed by satin weave processing, Be not limited to cutter grinding, for using with affected layer formation mirror finish be applied in aluminium base 12 in the case of and The problem of speech is common, can be solved by the anodic oxidation process and etching work procedure to preposition processing for carrying out foregoing.Mirror Within the processing of face, mechanical lapping (the Mechanical Polishing of grinding processing, attrition process etc.：MP), chemical grinding with Mechanical lapping and cmp (Chemical Mechanical Polishing：CMP), can be rotten with processing The formation of layer.Mechanical lapping, such as comprising polishing, abrasive band polishing, sandblasting polishing.In addition, substituted chemistry is ground, ground by electrolysis Mill with mechanical lapping and situation under, similarly with the formation of affected layer.Among this specification, " machinery Mirror finish ", not only MP and CMP, also contains electrolytic polishing and mechanical lapping and processing.

Before satin weave processing, using the etching solution of alkalescence, the surface that further can also enter to be about to aluminium base 12 is lost The process (following, also to there is the situation of referred to as " substrate surface etching work procedure ") at quarter.By using the base material table of the etching solution of alkalescence Facet etch process, can remove at least some of the affected layer of the aluminium base 12 for the reason for being likely to become grinding vestige.

The etching solution of alkalescence, such as comprising inorganic alkali (inorganic base) or organic alkali (organic base).Inorganic alkali, example Such as include potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide.Organic alkali, such as comprising the chemical combination with amido Thing.Organic alkali, such as comprising 2- ethylaminoethanols (monoethanolamine), 1 grade of hydramine, double (2- hydroxyls) alkene of dimethyl.The erosion of alkalescence Carve the pH value of liquid, for example, less than more than 10 12.The etching solution of alkalescence, is not limited to above-mentioned, for example, can also use known alkali The cleaning solution of property.

Foregoing substrate surface etching work procedure, for example, it is also possible to the anodic oxidation process of preposition processing and etching Carried out before process.Foregoing substrate surface etching work procedure, for example, it is also possible to replace the anodic oxidation process to preposition processing And etching work procedure is carried out.Foregoing substrate surface etching work procedure, because using the etching solution of alkalescence, it is possible to as degreasing Process.

By the way that substrate surface etching work procedure to be replaced to anodic oxidation process and etching work procedure to preposition processing, process number Mesh can be reduced.Substrate surface etching work procedure doubles as to reduce for the situation process number of degreasing process.By less Process, can obtain the aluminium base with uneven few surface.Can high efficient production to formed have appropriateness anti-glare The mould of the antireflection film of function.The manufacture yield of the antireflection film of anti-glare function with appropriateness is lifted.

Then, as shown in Fig. 1 (c), by forming inorganic material layer 16 on the surface of aluminium base 12, in inorganic material layer 16 On re-form aluminium film 18, make mould base material 10.

On the surface of aluminium film 18, formation is reflected to be resisted by be formed the surface satin weave processing of aluminium base 12 by reversion The structure of dazzle structure.Here, the structure that aluminium film 18 is formed is also referred to as by reversion anti-glare structure.On the surface of aluminium film 18 Be formed by reversion anti-glare structure, be formed on the surface of aluminium base 12 it is substantial by reversion anti-glare structure Same structure.Therefore, be formed on the surface of aluminium film 18 by reversion anti-glare structure, with multiple grand convex portion 18p with it is many Individual grand recess 18g.Grand convex portion 18p is substantially surrounded by grand recess 18g, grooves of the grand recess 18g as provided grand convex portion 18p peripheries As exist.

As the material of inorganic material layer 16, for example, it can use tantalum oxide (Ta₂O₅) or silica (SiO₂)。 Inorganic material layer 16, for example, can be formed by sputtering method.As inorganic material layer 16, the situation of tantalum oxide layers, oxidation are used The thickness of tantalum layer, for example, 200nm.

The thickness of inorganic material layer 16, preferably more than 100nm is less than 500nm.When inorganic material layer 16 thickness less than When 100nm, the situation that aluminium film 18 produces defect (mainly space, that is, crystallize the gap of intergranular) is had.In addition, when inorganic The thickness of material layer 16 is when more than 500nm, according to the surface state of aluminium base 12, between aluminium base 12 and aluminium film 18 Become easy by insulation.In order to by supplying electric current from the lateral aluminium film 18 of aluminium base 12 to carry out the anodic oxidation of aluminium film 18, need Want the flowing of electric current between aluminium base 12 and aluminium film 18.When using the composition that electric current is supplied from the inner face of cylindric aluminium base 12 When, can be by aluminium film 18 in whole surface anodic oxidation, and with anodic oxygen because electrode need not be set in aluminium film 18 The problem of supply of the progress electric current of change becomes difficult such will not also occur, and can do aluminium film 18 in whole surface uniformity Anodic oxidation.

In addition, the inorganic material layer 16 in order to form thickness, it is however generally that need film formation time is elongated.When film formation time becomes When long, the surface temperature of aluminium base 12 unnecessarily rises, and its result has the deterioration for the film for producing aluminium film 18, lacked Fall into the situation in (mainly space).If the thickness of inorganic material layer 16 can also just suppress like this not less than 500nm The generation of good state.

Aluminium film 18, for example, as being described in patent document 3, for be more than 99.99mass% using purity aluminium formed Film (following, also there is the situation for being referred to as " high-purity aluminium film ").Aluminium film 18, for example, using vacuum vapour deposition either sputter Method is formed.The thickness of aluminium film 18, preferably from about more than 500nm and about below 1500nm scope, for example, being about 1 μm.

In addition, as aluminium film 18, replacing high-purity aluminium film, can also using and be described in International Publication No. 2013/ The aluminium alloy film of No. 0183576.The aluminium alloy film of International Publication No. 2013/0183576 is described in, beyond aluminium, aluminium Metallic element and nitrogen.Among this specification, " aluminium film " is not only high-purity pure aluminium film, international public containing being recorded in yet Open the aluminium alloy film of No. 2013/0183576.To refer to, the disclosure that International Publication No. 2013/0183576 it is complete Portion is incorporated in this specification.

When using foregoing aluminium alloy film, the minute surface of reflectivity more than 80% can be obtained.Constitute aluminium alloy film Crystal grain, average particulate diameter when in terms of the normal direction of aluminium alloy film, for example, below 100nm, aluminium alloy film Maximum surface roughness R_maxFor below 60nm.The containing ratio of the nitrogen contained in aluminium alloy film, for example, being more than 0.5mass% Below 5.7mass%.The standard electrode potential of metallic element beyond the aluminium that aluminium alloy film contains, the normal electrode electricity with aluminium The poor absolute value of position is below 0.64V, and the containing ratio of the metallic element in aluminium alloy film is preferably more than 1.0mass% Below 1.9mass%.Metallic element, for example, being Ti either Nd.But, metallic element is not limited to these, the mark of metallic element Collimator electrode current potential, with the poor absolute value of the standard electrode potential of aluminium for below 0.64V other metallic elements (for example, Mn, Mg, Zr, V and Pb) can also.In addition, metallic element or Mo, Nb either Hf.Aluminium alloy film, can also contain this A little metallic elements is two or more.Aluminium alloy film, for example, being formed using DC magnetron sputter reactors method.The thickness of aluminium alloy film Preferably from about more than 500nm and about below 1500nm scope, for example, being about 1 μm.

Here, reference picture 3 (a)~(d), illustrates by reversion anti-glare structure.Fig. 3 (a), is to have to handle institute by satin weave (full size in microscopic iage is 15 to the laser capture microdissection mirror image on the surface for the aluminium base 12 by reversion anti-glare structure being formed μm), Fig. 3 (b) is that have the aluminium base 12 by reversion anti-glare structure formed by satin weave processing from vertical direction SEM pictures during surface (full size is 10 μm in SEM pictures).Fig. 3 (a) is observation with the anodizing temperature of experimental example described later 10 DEG C, the surface of the aluminium base 12 of satin weave processing is carried out under conditions of anodizing time 5min, Fig. 3 (b) is observation with aftermentioned Experimental example 10 DEG C of anodizing temperature, the table of the aluminium base 12 of satin weave processing is carried out under conditions of anodizing time 3min Face.Fig. 3 (c) is the floor map for being inverted anti-glare structure, and Fig. 3 (d) is the schematic perspective view for being inverted anti-glare structure.

To be formed as shown in Fig. 3 (a)~(d), handled by satin weave by reversion anti-glare structure, with multiple grand convex portions 18p and multiple grand recess 18g.Grand convex portion 18p is substantially surrounded by grand recess 18g, and grand recess 18g is as provided grand convex portion 18p Exist as the groove of periphery.

Multiple grand convex portions 18, when in terms of normal to a surface direction, although slightly there is greatly polygonal profile, still The systematicness of configuration is not seen.(area circle equivalent is straight for grand convex portion 18p two-dimensional when in terms of normal to a surface direction Footpath), it is below 30 μm of about more than 200nm.From Fig. 3 (a) microscopic iage and Fig. 3 (b) SEM pictures, the surface of grand convex portion 18 Two-dimensional when normal direction is seen, can be evaluated whether into less than more than about 1 μm about 5 μm.In addition, above grand convex portion 18, It is substantially flat.

It is the 10 of grand convex portion 18p two-dimensional by grand convex portion 18p grand recess (groove) 18g substantially surrounded width The size of 1/1 1 to 5th degree.Between adjacent grand recess 18g distance average value (it is average it is adjacent between apart from AD_int), It is that may be considered that the average value of two-dimensional when with terms of the normal to a surface direction of grand convex portion 18 is roughly equal. This because grand recess 18g by grand convex portion 18p substantially surround as be formed, adjacent grand recess 18g refers to providing grand convex portion The adjacent grand recess 18g meaning among the section in the direction of 18p two-dimensional.Therefore, it is average it is adjacent between apart from AD_int, with The average value of grand convex portion 18p two-dimensional is average value and roughly equal with grand recess 18g width.In addition, grand recess 18g depth AD_depth, for example can also be more than 20nm below 500nm, or more than 20nm is less than 5 μm.

After being formed by reversion anti-glare structure, anodic oxidation is alternately repeated with etching, by being tied by reversion moth eye The formation of structure, obtains the ophthalmically acceptable mould 100 of moth of Fig. 1 (d) signals.That is, formed by the process of reversion moth ocular structure, contain aluminium film 18 surface by anodic oxidation, the process of the formation of porous alumina layer 14 with multiple nick portion 14p, with after this, By making porous alumina layer 14 contact etching solution, process that multiple nick portion 14p of porous alumina layer 14 are expanded, with After this, further by anodic oxidation, make the process of multiple nick portion 14p growth.It is used in the electrolyte of anodic oxidation, example As being containing the sour aqueous solution among the group constituted selected from oxalic acid, tartaric acid, phosphoric acid, sulfuric acid, butyric acid, citric acid, malic acid. As etching solution, can use the organic acid or aqueous sulfuric acid of formic acid, acetic acid, citric acid etc., butyric acid phosphoric acid mixed aqueous solution, The either alkaline aqueous solution of sodium hydroxide, potassium hydroxide etc..

Anodic oxidation, with etching repeatedly a series of process, is preferably to be terminated with anodic oxidation process.By with anode Oxidation operation terminates (thereafter without etching work procedure), and nick portion 14p bottom can be made to diminish.It is thusly-formed by reversion moth eye The method of structure, for example, the International Publication No. of present inventor 2006/059686 is revealed.In order to refer to, International Publication The disclosure of No. 2006/059686 is fully incorporated in this specification.

For example, passing through anodization step (electrolyte：Oxalic acid aqueous solution (10 DEG C of concentration 0.3mass%, fluid temperature), Applied voltage：80V, additional time：55 seconds) and etching step (etching solution：Phosphate aqueous solution (10mass%, 30 DEG C), etching Time：20 points) it is alternately many (such as 5 times for several times：Anodic oxidation 5 times and etching 4 times) it is repeated, can as shown in Fig. 1 (d) Obtain the ophthalmically acceptable mould 100 of moth of the porous alumina layer 14 with nick portion 14p.With institute under conditions of illustrating in this as example The porous alumina layer 14 of formation, such as reference picture 17 (c) it is illustrated, with by D_p=D_intIt is more than 10nm less than 500nm, D_depthThe structure of arrangement is not advised densely less than the nick portion 14p of 1000nm (1 μm) degree for more than 10nm.Nick portion 14p is omited It is adjacent in the form of forming saddle to be coniform.

Moth ocular structure is inverted by what nick portion 14p was configured, anti-glare structure is overlapped in and is formed.Therefore, Such as Fig. 1 (d) is showed schematically, be there are and is formed at the nick portion 14p for the grand convex portion 18p for constituting anti-glare structure, with being formed at Grand recess 18g nick portion 14p.Grand convex portion 18g nick portion 14p is formed at compared with the nick portion 14p for being formed at grand convex portion 18p It is deeper.

Also, under nick portion 14p, barrier layer is formed, porous alumina layer 14 is by with many of nick portion 14p Aperture layer, constituted with being present under porous layer the barrier layer (recess 14p bottom) of (aluminium film side).Adjacent nick portion 14p Interval (distance between centers), be known to be substantially 2 times of the thickness equivalent to barrier layer, voltage during with anodic oxidation is substantially It is proportional.In addition, under porous alumina layer 14, among aluminium film 18, there are not anodized aluminium rest layers 18r.

Fig. 4 A (a) are SEM picture of the signal from vertical direction during the surface of the aluminium film 18 of mould base material 10 (in SEM pictures Full size is 10 μm), Fig. 4 A (b) are that signal is inverted moth ocular structure from vertical direction with the ophthalmically acceptable mould 100 of moth SEM pictures during the surface of porous alumina layer 14 (full size is 10 μm in SEM pictures).Fig. 4 A (a) mould base material 10, is in tool There is the aluminium by reversion anti-glare structure by being formed with the processing of the satin weave of the similarity condition of aluminium base 12 shown in Fig. 3 (b) On base material 12, thickness about 200nm tantalum oxide layers and thickness about 800nm and the aluminium film (aluminium alloy film) containing Ti and N are formed with 18 mould base material 10.The Ti containing ratios of aluminium film 18 are about 1.0mass%, N containing ratios be about more than 1.2mass% about Below 2.0mass%, remaining is Al and inevitable impurity.Fig. 4 A (b) the ophthalmically acceptable mould 100 of moth, is to use and Fig. 4 A (a) the mould base material 10 that the mould base material 10 shown in is made with the same terms, with the condition illustrated previously as example, passes through sun Pole is aoxidized and etching alternately (anodic oxidation 5 times with etching 4 times) repeatedly be produced ophthalmically acceptable mould 100 of moth of progress.

It is apparent that on the surface of aluminium film 18, reflecting the surface of aluminium base 12 during as Fig. 4 A (a) being compared with Fig. 3 (b) The structure by reversion anti-glare structure be formed.In addition, it is apparent that moth is ophthalmically acceptable during as Fig. 4 A (b) being compared with Fig. 4 A (a) The porous alumina layer 14 of mould 100, with the overlapping surface texture by reversion moth ocular structure on by reversion anti-glare structure.

Consequently, it is possible to which according to the manufacture method of the ophthalmically acceptable mould 100 of moth of embodiment of the present invention 1, can manufacture to form The ophthalmically acceptable mould 100 of moth of antireflection film with anti-glare function.On with preventing for being formed using the ophthalmically acceptable mould 100 of moth The anti-glare function of reflectance coating, is described in detail after being shown in experimental example.

(embodiment 2)

The manufacture method of the mould of embodiment of the present invention 2, among process (B), the manufacture method with the mould of embodiment 1 It is different.The manufacture method of the mould of embodiment 2, replaces the process (B) of the manufacture method of the mould of embodiment 1, includes general The process (process (B ')) that the surface of aluminium base is handled by alkaline etching liquid satin weave.That is, among embodiment 2, substitution contains There is the aqueous solution of the salt of hydrogen fluoride and ammonia, using alkaline etching liquid, the surface satin weave of aluminium base is handled.

Among the process that the surface of aluminium base is handled by alkaline etching liquid satin weave, the processing that can remove aluminium base is gone bad At least some of layer.Handled and other process as satin weave, it is not necessary to enter to be about to the process of the surface etching of aluminium base, or It is the anodic oxidation process and etching work procedure to preposition processing.In addition, the surface of aluminium base by alkaline etching liquid satin weave at The process of reason, can double as being degreasing process.When by the manufacture method of the mould of embodiment 2, manufacture work is not increased Sequence, it is possible to manufacture the mould of the antireflection film to form the anti-glare function with appropriateness.

The structure of the mould manufactured on the manufacture method of the mould of embodiment 2 and by manufacture method so, ginseng Illustrate according to Fig. 4 B (a)~(c).The manufacture method of the mould of embodiment 2, in addition to process (B ') or with ginseng Manufacture method according to the mould of the embodiment 1 illustrated by Fig. 1~Fig. 4 A is identical.On the reality illustrated with 1~Fig. 4 of reference picture A The manufacture method and the structure of the mould manufactured by manufacture method so for applying the mould of mode 1 substantially identical portion Part, omit the description.

Fig. 4 B (a), are to have the profile showed schematically by the surface structure of the aluminium base 12 of reversion anti-glare structure, Fig. 4 B (b), are the diagrammatic cross-sections that inorganic material layer 16 and the mould base material 10 of aluminium film 18 are formed with the surface of aluminium base 12, Fig. 4 B (c) be with by with alkalescence etching solution carry out satin weave processing formed by by the aluminium base of reversion anti-glare structure The laser capture microdissection mirror image on 12 surface.

The surface of aluminium base 12, is handled by using the etching solution satin weave of alkalescence, shown in such as Fig. 4 B (a)~(c), in aluminium base The surface 12s of material 12 is formed with by reversion anti-glare structure.Grand recess 12g, when in terms of normal to a surface direction, be, for example, The region (such as comprising circle substantially) closed with curve.Grand recess 12g shape, for example, can also be substantially hemisphere.It is grand recessed Portion 12g in terms of normal to a surface direction when two-dimensional (area equivalent circle diameter), for example, more than 500nm and 20 Below μm.By multiple grand recess 12g with mutually different two-dimensional, formed by reversion anti-glare structure.

Carried out using the aqueous solution of the salt containing hydrogen fluoride and ammonia of the manufacture method of the mould of embodiment of the present invention 1 When satin weave processing, reference picture 3 (a)~(d) as previously discussed, formed have the big slightly grand recess 12g of polygonal profile, 18g.The reason for grand recess 12g is the region by multiple substantially linear closings, it is considered to be due to corresponding to aluminium base 12 Grain boundary and be formed with grand recess 12g.

Grain boundary refers to, the interface that crystallization intergranular adjacent each other is present among polycrystalline body (such as metal).This theory In bright book, it is assumed that to contain crystal grain (grain) and sub- crystal grain (subgrain) in the crystal grain of aluminium base, in aluminium base Grain boundary contains grain boundary (grain boundary) and sub- grain boundary (subgrain boundary).This specification In, the crystal grain of aluminium base is from about tens of μm to approximate number mm person containing size.

In contrast, when carrying out satin weave processing using the alkaline etching liquid of the manufacture method of the mould of embodiment 2, Form the grand recess 12g for example with the region closed with curve.When being regarded as using alkaline etching liquid, aluminium base 12 Grain boundary can form grand recess 12g with being less affected.

In general, when using acidic etching liquid, thering is the grain boundary corresponding to the aluminium base being etched to form grand The tendency of recess, in contrast, when using alkaline etching liquid, has and is etched the crystal grain and grain boundary of aluminium base less Can be affected can form the tendency of grand recess.When carrying out satin weave processing using alkaline etching liquid, it is believed to suppress The etching produced due to the crystal grain and grain boundary of aluminium base 12 it is uneven.At by alkaline etching liquid satin weave Film formed by the manufactured mould of reason, can suppress to produce due to crystal grain and grain boundary is uneven.Therefore, it is real The manufacture method of the mould of mode 2 is applied, the manufacture for the mould to form antireflection film is suitably used in.

But, the experimental example as after is schematically illustrate, because the species of alkaline etching liquid, on the surface of aluminium base, also can There is the situation to form the concaveconvex shape (also have be referred to as pattern situation) more than grand recess.As be described hereinafter, for example, by suitably adjusting The concentration for the alkali that the pH value or alkaline etching liquid of whole alkaline etching liquid contain, can suppress the concaveconvex shape more than grand recess Generation.

Among this specification, the satin weave treatment process on the surface of aluminium base refers to, forms anti-on the surface of aluminium base Turn the process of anti-glare structure.It is excellent in order to form the antireflection film with appropriate anti-glare function as after illustrated by experimental example Elect as, the process by the way that the surface of aluminium base is handled by alkaline etching liquid satin weave, by the arithmetic average on the surface of aluminium base Roughness Ra is such as more than 50nm and below 200nm.

The etching solution of alkalescence, for example, including inorganic alkali (inorganic base) or organic alkali (organic base).Inorganic alkali, For example, including potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide etc..Organic alkali, such as comprising the change with amido Compound.Organic alkali, such as comprising 2- ethylaminoethanols (monoethanolamine), 1 grade of hydramine, double (2- hydroxyls) alkene of dimethyl.Alkalescence Etching solution, is not limited to described above, can also use the cleaning solution of known alkalescence.By the washing using known alkalescence Liquid, can suppress the formality of satin weave treatment process and/or the increase of cost.

In addition, the manufacture method of the mould of embodiment of the present invention, is not limited to use alkaline etching liquid person, can also use Acidic etching liquid.For example, the condition of composition and/or processing method according to aluminium base etc., even with acidic etching liquid, also can There is the inapparent situation of crystal grain and grain boundary of aluminium base.In addition, by suitably adjusting the acid that acidic etching liquid is included Species and/or acid concentration etc. condition, the erosion produced due to the crystal grain and grain boundary of aluminium base can be suppressed That carves is uneven.

(manufacture method of antireflection film and the structure by the mould manufactured by its manufacture method)

Next, reference picture 5, illustrates using the moth manufactured by embodiment 1 or the manufacture method of the mould of embodiment 2 The manufacture method of the antireflection film of ophthalmically acceptable mould 100.Fig. 5 is the method for illustrating to manufacture antireflection film by roll-to-roll mode Diagrammatic cross-section.

First, the cylindric ophthalmically acceptable mould 100 of moth is prepared.In addition, the cylindric ophthalmically acceptable mould 100 of moth, with above-mentioned system Method is made to be manufactured.

As shown in figure 5, surface to be endowed to the machined object 42 of ultraviolet hardening resin 32 ', the ophthalmically acceptable mould of moth is pressed into In the state of 100, by hardening ultraviolet hardening resin 32 ' in the irradiation ultraviolet radiation of ultraviolet hardening resin 32 ' (UV).As Ultraviolet hardening resin 32 ', for example, can use acrylic resin.Machined object 42, e.g. TAC (Triafol T) Film.Machined object 42, from release roller release (not shown), thereafter, be coated with etc. for example, by slit on surface assign it is ultraviolet Line hardening resin 32 '.Machined object 42, as shown in figure 5, being supported by support roller 46 and 48.Support roller 46 and 48, with rotation Rotation mechanism, transports machined object 42.In addition, the cylindric ophthalmically acceptable mould 100 of moth, with the travelling speed corresponding to machined object 42 Rotary speed, Fig. 5 toward arrow signal direction rotated.

Thereafter, by the ophthalmically acceptable mould 100 of moth being separated from machined object 42, the concavo-convex knot of the ophthalmically acceptable mould 100 of moth has been transferred The hardening nitride layer 32 of structure (by reversion moth ocular structure) forms the surface in machined object 42.Hardening nitride layer 32 is formed with surface Machined object 42, is wound from take-up roll (not shown).

Fig. 6 (a) and (b), is the SEM pictures of signal antireflection film manufactured as described above.Fig. 6 (a) and (b), is this The SEM pictures of the antireflection film with anti-glare function of invention embodiment, Fig. 6 (a) is the antireflection film from vertical direction Surface when SEM pictures (in SEM pictures full size be 10 μm), Fig. 6 (b) is the section of antireflection film and surface from tilted direction When SEM pictures (in SEM pictures full size be 3 μm).

It was found from Fig. 6 (a) and (b), moth ocular structure has been overlapped to form in anti-glare structure.Anti-glare structure, is by leading to Cross grand recess and grand convex portion composition that the grand convex portion 18p and grand recess 18g of satin weave processing formation are each inverted.Conduct from there Two-dimensional when the grand recess surface normal direction of composition anti-glare structure of example signal is seen, be more than about 1 μm and Less than about 5 μm, the two-dimensional for being the grand convex portion for constituting anti-glare structure is the size of 1/1 to five/10ths degree. It is about more than 200nm and about below 500nm in addition, constituting the height of the grand convex portion of anti-glare structure.On constituting moth ocular structure Grand convex portion, two-dimensional and it is adjacent between distance (correspond to D_P=D_int) about 200nm, height is (corresponding to D_depth) about 200nm.

Reference picture 7 (a)~(c), illustrates the structure of the antireflection film 32 with anti-glare function of embodiment of the present invention. Fig. 7 (a)~(c) is the schematic diagram of the antireflection film 32 with anti-glare function of embodiment of the present invention, Fig. 7 (a) be from Vertical direction observes the schematic diagram during surface of antireflection film 32, when Fig. 7 (b) is the surface of antireflection film 32 from tilted direction Schematic diagram, Fig. 7 (c) is the diagrammatic cross-section of antireflection film 32.

Among Fig. 7 (a)~(c), multiple dimpling portions of moth ocular structure are constituted, contain dimpling portion 32p and 32g.Dimpling portion 32p formation is constituting the nick portion of anti-glare structure, and 32g formation in dimpling portion is in the dimpling portion of composition anti-glare structure.Therefore, it is micro- Convex portion 32g, higher than dimpling portion 32p, and is configured to will be formed in the dimpling portion 32p of grand convex portion and substantially surrounds.This is corresponded to In the ophthalmically acceptable manufacturing process of mould 100 of moth, handled by satin weave to be formed by among reversion anti-glare structure, grand convex portion 18p Substantially it is surrounded by grand recess 18g.When watching Fig. 6 (a) and (b) microscopic iage, it is considered as being formed compared with these Higher dimpling portion, most dimpling portions is surrounded.

Then, reference picture 8, illustrate that the diffusing reflection of the antireflection film with anti-glare function of embodiment of the present invention is special Property.Fig. 8 (a) is the measurement result figure for representing the light diffused the distribution that the antireflection film with anti-glare function is caused Table, Fig. 8 (b) is to represent the measurement system schematic diagram that the light diffused is distributed.Scattering is not particularly intended to exclude in addition, diffusing Light.

Among Fig. 8 (a), EX.1 be represent embodiment of the present invention the antireflection film with anti-glare function it is unrestrained The light distribution of reflected light.This antireflection film, be by with experimental example described later similarly with the aqueous solution containing ammonium acid fluoride The aluminium base 12 that (concentration of ammonium acid fluoride is 4mass%) has carried out satin weave processing 10 DEG C, 4 minutes uses to be formed as mould Anti-glare film.CNV.1 represents that the having for plated resin formation that the above-mentioned use of reference picture 17 contains delustering agent is put down with nothing The light diffused the distribution of the antireflection film of the anti-glare structure on the surface of the continuous waveform in smooth portion.CNV.1's is anti-dizzy The two-dimensional of photo structure is 10 μm~30 μm, height 500nm~1000nm.

The light distribution diffused, shown in such as Fig. 8 (b), relative to sample film, with 5 ° of light irradiation of incidence angle, with 0 °~25 ° of acceptance angle determines the light distribution diffused.Specifically, each sample film is attached to glass plate, to survey Angle photometric determination light distribution.As goniophotometer, the GP-200 of color technical research institute in village is used.Here, table Show and set incidence angle as 5 °, take acceptance angle as transverse axis, the maximum of the intensity that diffuses as 80% it is normalized take it is relative The common logarithm of diffusing reflection rate (%) as the longitudinal axis light distribution curve.As long as directional spreding curve as shown below is without especially saying It is bright, also to be identical.

CNV.1 light distribution, in acceptance angle, 5 ° obtain peak value, in the range of being converged in acceptance angle from 0 ° to 10 °. CNV.1 light distribution curve, it is all for be relatively suddenly higher, relative diffusing reflection rate (%), with being offset from 5 ° of acceptance angle Successively decrease.Existing antireflection film (CNV.1), although haze value is low to arrive about 3, specular reflective is low, image blurring.Therefore, especially When being the image display panel for being used in fine, the impression of display quality decline is given.

On the other hand, EX.1 light distribution curve, in acceptance angle, 5 ° obtain peak value, about 3 °~4 ° of acceptance angle and light The change of the EX.1 for the scope that about 6 °~7 ° of angle relative diffusing reflection rate (%), although the relative diffusing reflection rate compared with CNV.1 (%) is more anxious high, the change of EX.1 of the acceptance angle about less than 3 ° and acceptance angle about more than 7 ° relative diffusing reflection rate (%), compared with CNV.1 relative diffusing reflection rate (%) more relaxes.EX.1 is although haze value about 15, higher compared with CNV.1, but in specular reflective It is excellent.The experimental example illustrated as be described hereinafter, the antireflection film (EX.1) by embodiment of the present invention with anti-glare structure, because Inclination with light distribution curve is that the point discontinuously changed is present in acceptance angle more than 0 ° in less than 10 ° of scope, And relative diffusing reflection rate (%) so diffusing characteristic diffuser of feature in 1% and above less than 10% scope, it is and existing Antireflection film (CNV.1) compares, high with specular reflective, and (such as haze value is about more than 7 for the diffusing reflection function of appropriateness And about less than 24).The antireflection film (EX.1) of embodiment of the present invention, even if for example, being used in more than 300ppi fines Display, is pressed down imaged Over degree and obscured, can provide the display for being suppressed reflection with high display quality.

Hereinafter, as shown in experimental example, by the manufacture method of the ophthalmically acceptable mould of the moth of embodiment of the present invention and the ophthalmically acceptable mould of moth It is further described.

[selection of aluminium base]

The aluminium alloy of Al-Mg systems

As the aluminium alloy of Al-Mg systems, JIS A5052 are used.

JIS A5052 have composition (mass%) as described below.

Si：Less than 0.25%, Fe：Less than 0.40%, Cu：Less than 0.10%, Mn：Less than 0.10%, Mg：2.2~ 2.8%th, Cr：0.15~0.35%, Zn：Less than 0.10%, other：Individually below 0.05%, entirety less than 0.15%, residue Partly：Al.

The cylindric aluminium base with JIS A5052 aluminium alloy formation is used to make mould base material.Here, using not right The aluminium base made with duct method applies cold-drawn processing, and passes through the aluminium base of cutter grinding progress mirror finish.In addition, mould Base material, reference picture 1 (a) is made by such as above-mentioned method.As inorganic material layer, thickness 200nm tantalum oxide layers are formed, as Aluminium film, forms the aluminium alloy film that thickness 800nm contains Ti and N.The Ti containing ratios of aluminium alloy film are in about 1.0mass%, N containing ratio In about more than 1.2mass% below 2.0mass%, remaining is Al and inevitable impurity.As long as being recorded without special, on The experimental example of signal as described below is also identical.

The satin weave processing of chemistry is carried out in aluminium base.As the etching solution handled to satin weave, using containing ammonium acid fluoride The aqueous solution (concentration of ammonium acid fluoride be 4mass%).The grand concaveconvex structure of gained, necessary coarse, diffusing reflection performance above It is high, appropriate anti-glare function can not be obtained.

Here, the condition that satin weave is handled relaxes (short time of processing, the low concentration for the treatment of fluid, treatment temperature Low temperature) when, it was observed that surface is uneven.Specifically, the low region of diffusing reflection performance is produced in several centimetres of grades With high region.

Due to above reason, it is judged as being not suitable for the aluminium base of the aluminium alloy formation of Al-Mg systems.

The aluminium alloy of Al-Mg-Si systems

As the aluminium alloy of Al-Mg-Si systems, JIS A6063 are used.JIS A6063 have composition (mass%) as described below.

Si：0.20~0.60%, Fe：Less than 0.35%, Cu：Less than 0.10%, Mn：Less than 0.10%, Mg：0.45~ 0.9%th, Cr：Less than 0.10%, Zn：Less than 0.10%, Ti：Less than 0.10%, other：It is all individually below 0.05% Less than 0.15%, remaining part：Al.

The cylindric aluminium base with JIS A6063 aluminium alloy formation is used to make mould base material.Here, using not right The aluminium base made with duct method applies cold-drawn processing, and passes through the aluminium base of cutter grinding progress mirror finish.

This aluminium base carries out satin weave processing with the aqueous solution containing ammonium acid fluoride.Except the aluminium base that is made with duct method It is not uneven in plane outside seam, you can to obtain the grand concaveconvex structure of the anti-glare function with appropriateness.

Then, carry out the aluminium base of mirror finish to contain ammonium acid fluoride by cutter grinding after cold-drawn processing is applied The aqueous solution carry out satin weave processing when after, seam part is not also unobtrusively, uneven in plane, you can obtain with appropriateness The grand concaveconvex structure of anti-glare function.

Thus, as aluminium base, the aluminium alloy of Al-Mg-Si systems is particularly preferably with JIS A6063 formers.Especially It is to apply the aluminium base of cold-drawn processing, seam is unobtrusively so therefore preferred.Even if in addition, hot extrusion method, because with heart axle The aluminium base that method makes does not have seam, so, can suitably use identically with the aluminium base made with cold-drawing process.

Fig. 9 (a)~(c), is the surface that signal carries out satin weave processing ground aluminium base with the aqueous solution containing ammonium acid fluoride SEM pictures (5000 times, the full size in SEM pictures is 10 μm).SEM pictures, use electric field radioactive SEM (Hitachi's system S-4700) obtain.Following SEM pictures are also identical.

Fig. 9 (a), is the SEM pictures on the surface of the aluminium base for the JIS A6063 for applying cold-drawn processing, Fig. 9 (b) is not apply The SEM pictures on the surface of the JIS A6063 of cold-drawn processing aluminium base, Fig. 9 (c) is the JIS A5052 for not applying cold-drawn processing The SEM pictures on the surface of aluminium base.Any one, the time of satin weave processing is carried out with the aqueous solution containing ammonium acid fluoride, is 45 seconds. But, on Fig. 9 (a), as preposition processing, carry out degreasing and washing.On Fig. 9 (b) and Fig. 9 (c), preposition place is used as Reason, has carried out anodic oxidation and etching.On being described after the effect of these preposition processing.

Fig. 9 (a) and (b), substantially learn when such as being compared with Fig. 9 (c), the surface (Fig. 9 (c)) of JIS A5052 aluminium base, The surface (Fig. 9 (a) and (b)) of aluminium base compared with JIS A6063, is formed with very coarse concaveconvex structure.Therefore, as aluminium The aluminium alloy of base material, preferably Al-Mg-Si systems, particularly JIS A6063.

[degreasing washing]

When the JIS A6063 of cold-drawn processing aluminium base progress satin weave processing is applied with, it can be produced on the surface of aluminium base It is raw grand uneven.In order to prevent such grand uneven generation, the preposition processing handled as satin weave has carried out degreasing With the discussion of washing.

In degreasing, the concentration using inorganic alkaline remover (L.G.L of Yokohama oil prodution industry limited company) is The 3mass% aqueous solution, sample was impregnated in this aqueous solution with 40 DEG C, 10 minutes.Thereafter, by the way that sample is impregnated into 10 in pure water Minute washs.Prepare the sample after the washing of standing time different (0 point, 5 points, 15 points, 22 hours) in atmosphere, its is laggard The processing of row satin weave.

Although the surface for not drying the aluminium base with regard to carrying out satin weave processing after washing fully does not produce uneven (following institute State the condition C 1 and C2 of table 1), the surface that the aluminium base for once carrying out satin weave processing afterwards is dried after washing is considered as universally uneven Even (condition C 4).It is observed slightly uneven (condition C 3) when 15 points of standing time.

When washing re-dry after degreasing, on the surface of aluminium base, the aluminium hydroxide of the solid of precipitation causes set. This aluminium hydroxide causes to hinder treatment fluid in the result of the surface action of aluminium base, is considered as generation uneven.Therefore, wash Afterwards, it is preferably before the dry tack free of aluminium base, to carry out satin weave processing.Certainly, if being washed once again after drying, then at it If carrying out satin weave processing before drying, uneven generation can be prevented.It is preferably to expire it at 15 minutes after washing procedure Preceding progress satin weave processing.

In addition, as the medicament of degreasing, can also use interfacial agent (solar corona chemistry limited company Niccasan clean) or sulfuric acid.

[table 1]

[time of satin weave processing]

Illustrate that the time of satin weave processing is with overflowing in order to make to be formed the moth ophthalmically acceptable mould with anti-glare function antireflection film The discussion result of relation between the degree of reflecting properties.In following experiment, the aluminium for applying cold-drawn processing JIS A6063 is used Base material.As the etching solution handled to satin weave, using the aqueous solution containing ammonium acid fluoride, (concentration of ammonium acid fluoride is 4mass%).

The time handled for aluminium base satin weave is made with the mould sample of 5 seconds~3 points changes.The temperature of satin weave processing is made For 35 DEG C.In addition, before carrying out satin weave processing, degreasing is carried out using interfacial agent, until before 15 minutes expire after washing Carry out satin weave processing.

Be applied with satin weave processing aluminium base surface coat releasing agent (Daikin Industries, Ltd. Optool DSX) after, the ultraviolet hardening resin of acrylic acid series is coated, with the state irradiation ultraviolet radiation transferred in PET film Harden it.Using the sample film with grand concaveconvex structure of acquisition, the method illustrated with reference picture 8 (b) determines light point Cloth.Sample film as used herein, like this do not have moth ocular structure, only have anti-glare structure film, have by The referred to as situation of anti-glare film.

In addition, as with reference to sample film, applicant have evaluated in the lump is used in a variety of anti-dizzy of television applications The light distribution of optical thin film (REF_No.1~No.4).Anti-glare film herein, is by coating distribution in film surface There is the coating agent (resin) of fine particle and formed, pass through what is formed with the grand concavo-convex surface with fine particle formation The diffusing reflection (including scattering) at the interface between diffusing reflection and coating agent and particulate, to show anti-glare function.The opposing party Face, reference picture 8 (a) illustrates the antireflection film (EX.1) or the anti-glare film illustrated below of embodiment of the present invention, only passes through tool There is grand convex-concave surface structure performance anti-glare function.

Figure 10 A are to represent the measurement result that the light diffused is distributed.Figure 10 A are also similar with Fig. 8 (a), expression set into Firing angle is 5 °, takes acceptance angle as transverse axis, and the maximum of the intensity that diffuses normalized takes relative diffusing reflection as 80% The common logarithm of rate (%) as the longitudinal axis light distribution curve.

From Figure 10 A result, it is known that as the time that satin weave is handled is elongated, the ratio regular meeting diffused of acceptance angle greatly Increase.That is, the time handled with satin weave is elongated, and anti-glare function is uprised.Haze value about 7 during 37 seconds processing times, 45 seconds When haze value about 10,75 seconds when haze value about 24, the haze value about 40 at 90 seconds.REF_No.1 haze value about 2, REF_ No.3 haze value about 40, is maximum in REF.In addition, haze value is the mist using electricity Se Industries, Incs of Japan Instrument NDH2000 is spent, is tried to achieve from (diffusing transmission rate/total light transmittance) × 100.

In below the 30 seconds time of satin weave processing, the change of the light distribution diffused is small, and anti-glare effect does not almost have Have.Even if in addition, the light distribution that the time of satin weave processing more than 90 seconds, diffuses almost does not change, will not increase again Anti-glare effect more than herein.From the viewpoint of anti-glare function, the time of satin weave processing can be described as preferably more than 30 seconds And less than 90 seconds.

More than the 37 seconds time of satin weave processing and the light diffused the distribution of the sample of the scope of less than 75 seconds, have The point that the inclination of light distribution curve discontinuously changes is present in acceptance angle more than 0 ° and in less than 10 ° of scope, and phase To diffusing reflection rate (%) so feature more than 1% and in less than 10% scope.Specifically, the light of these sample films The inclination of line distribution curve, is that (inclined absolute value is not for the discontinuously change of about 2 °~about 3 ° and about 7 °~8 ° of acceptance angle Continuously diminish).Being aware of these sample films has the same of appropriate anti-glare function (haze value about more than 7 about less than 24) When, it may have appropriate specular reflective.

Reference picture 10B, illustrates the assessment result of anti-glare function and specular reflective.Figure 10 B are signals based on above-mentioned The measurement result of the light distribution diffused, observes via each sample film and illustrates appearance during white black pattern to lead to ORG Cross the result for being calculated and being tried to achieve with simple simulation.That is, the position equivalent to the glass plate in Fig. 8 (b) is configured to above-mentioned white black Pattern state among, try to achieve diffuse light distribution.

CNV.1, is used in the result after the light distribution diffused shown in Fig. 8 (a) is calculated, E30, E45, E60 and E90, is that, using the result after the light distribution diffused shown in Figure 10 A is calculated, numeral represents that satin weave is handled respectively Time.

Figure 10 B each region with white black pattern shown in ORG, is made up of 233 units (equivalent to pixel).Observation is each The intensity that the light of observer's eyes is reached when unit is tried to achieve as following.

For example, it is contemplated that n-th of unit.The intensity of the light of observer's eyes is reached when observing each n-th of unit, be by The intensity for the light that n-th of unit is projected is multiplied by the value of the relative diffusing reflection rate (%) of 0.0 ° of above-mentioned light distribution curve, adds (n-1)th and n+1 unit intensity of light for projecting be multiplied by 0.1 ° of relative diffusing reflection rate (%) of above-mentioned line distribution curve Value, further, add n-th -2 and the intensity of light that projects of n+2 unit be multiplied by 0.2 ° of above-mentioned line distribution curve relatively unrestrained As the value of reflectivity (%), tried to achieve as the intensity totalling value of the light of 50 units injection from the both sides of n-th of unit.

Learnt when the CNV.1 for such as seeing Figure 10 B, the boundary line of B＆W is fuzzy to be clearly identified.Such one Come, the CNV.1 antireflection film with diffusing reflection function, although haze value is 3 or smaller, specular reflective is low, causes image It is fuzzy.

On the other hand, on Figure 10 B E45~E60 sample film (anti-glare film), the boundary line of B＆W can be with Clearly recognize.In addition, the point of anti-glare function refers to, the width in the grey region in black region is invaded, can more than CNV.1 Say it is that anti-glare function is high.

In E30 sample film, specular reflective too high result, the boundary line of B＆W is clearly recognized.In addition, In E90 sample film, specular reflective too low result, the boundary line of B＆W can not be clearly identified.This is, fully The result with visually observing subjective evaluation is corresponded to the pass, appropriate anti-glare function is had and appropriate minute surface is anti-to obtain The antireflection film (antireflective surfaces) of penetrating property, above-mentioned satin weave processing time is preferably more than 30 seconds and less than 75 seconds.

However, sample film of the satin weave processing time for the scope more than 30 seconds and less than 90 seconds, because having appropriate The specular reflective of anti-glare function and appropriateness, for example, be used in more than the display of the fine more than 300ppi, necessity Ground suppresses the fuzzy of image.

In addition, satin weave processing the preferred time can be according to treatment fluid concentration or proper temperature optimization.For example, as containing There is the aqueous solution of hydrogen fluoride and ammonia, using the situation of the aqueous solution containing 5mass% ammonium fluorides, by being carried out with 25 DEG C, 120 seconds Satin weave processing, can be obtained and the example (processing time 45~60 using the aqueous solution containing ammonium acid fluoride above-mentioned 4mass% Second) suitable result.

When the time of satin weave processing is short, because there is the possibility that problem is produced to volume production stability, it is preferably, output Amount carries raw volume production stability (controlling) in the range of being not less than more than necessary.Here, inquiring into by reducing the temperature that satin weave is handled Degree, the time of elongated satin weave processing.

Reference picture 11, illustrates the concentration 4mass% satin weave processing among 10 DEG C of the aqueous solution containing ammonium acid fluoride When, the relation between the time of satin weave processing and the light distribution diffused.

As known to from Figure 11, the sample film of more than 30 seconds processing time 2 point and less than 8 points of scope diffuses Light is distributed, in the range of the REF_No.1~No.4 light diffused distribution, even if treatment temperature declines, by lengthening Processing time, the resisting with antiglare property energy of a variety of anti-glare films almost covered in existing use can be formed by knowing The surface (anti-glare structure) of glare properties.That is, 10 DEG C, appropriate processing time are dropped to from 35 DEG C by treatment temperature, can From the scope more than 30 seconds and less than 90 seconds, to be expanded to the scope of 2 points of more than 30 seconds and less than 8 points.So will processing temperature Degree declines, and can obtain the enough and to spare such as the time of satin weave processing can become big advantage.

In addition, when the concentration of the ammonium acid fluoride aqueous solution is less than 4mass%, crystal grain becomes obvious, and also having to assign Give the situation of appropriate anti-glare function.Therefore, the concentration of the ammonium acid fluoride aqueous solution used in satin weave processing is preferably More than 4mass%.

The upper limit of the concentration of the ammonium acid fluoride aqueous solution is not particularly limited, but can be whether there is when because of more than 19mass% The risk with the irreflexive surface of appropriateness is made in method, so the concentration of the ammonium acid fluoride aqueous solution is preferably below 19mass%.

[suppression of the influence of the grinding vestige of aluminium base]

When the aluminium base for carrying out mirror finish to not applying cold-drawn processing with cutter grinding applies satin weave processing, have in aluminium The surface of base material is formed with the situation of grinding vestige.This grinding vestige is considered as due to by with cutter grinding mirror finish The etching for the affected layer being formed on the surface of aluminium base it is uneven.Therefore, grinding vestige is formed by satin weave processing The problem of, cutter grinding is not limited, in the case of the aluminium base of application mirror finish with using the formation with affected layer The problem of having common.In addition, when applying cold-drawn processing, because the processing that all plastic deformations for covering aluminium base are caused becomes The formation of matter layer, is reduced so being considered as the influence that mirror finish thereafter causes.

A variety of discussion result, it is known that before the aqueous solution satin weave processing containing hydrogen fluoride and the salt of ammonia, carry out To the anodic oxidation process and etching work procedure of preposition processing, grinding vestige can be lowered.That is, by that will be applied by cutter grinding Plus the surface anodization of mirror finish, by the way that the anode oxide film formed to be etched to removal, the surface of aluminium base is formed Grinding vestige can be reduced.

In addition, anodic oxidation, is preferably to use aqueous sulfuric acid as electrolyte.Because using aqueous sulfuric acid when Wait, compared with the situation using oxalic acid, the anode oxide film of softness can be obtained, so for example by phosphate aqueous solution, can be easy Ground is removed.Using the anodic oxidation of aqueous sulfuric acid, for example, it is preferable to for 20 DEG C, fixed current 115A/m², across 24 point 30 Second is carried out.Anodizing time than this it is shorter when, have the situation that grinding vestige is formed.

Using do not apply cold-drawn process, with by cutter grinding carry out mirror finish aluminium base (JIS A6063) and make The mould base material of work is used for the result of the experimental example carried out in following presentation.

Figure 12 (a), is that signal uses oxalic acid aqueous solution (concentration：0.3mass%) after anodic oxidation (80V, 5 DEG C, 10 points), Use phosphate aqueous solution (concentration：10mass%) aluminium base after etching (30 DEG C, 90 points) SEM pictures (5000 times, in SEM pictures Full size be 10 μm) figure, Figure 12 (b), be signal use aqueous sulfuric acid (concentration：17mass%) anodic oxidation is (fixed Electric current 115A/m², 20 DEG C, 24 points 30 seconds) after, use phosphate aqueous solution (concentration：10mass%) after etching (30 DEG C, 12 points) The figure of the SEM pictures (5000 times, the full size in SEM pictures is 10 μm) of aluminium base.

As known to from Figure 12 (a), on the surface of the aluminium base using oxalic acid anodizing, multiple recesses are formed.This It is that, because the oxide-film formed by using oxalic acid anodizing is hard, etching is difficult, therefore with oxide-film still some remaining State, be etched at leisure.Now, the surface of oxide film dissolving is being gone to carry out potential difference corrosion, its result is considered as forming Multiple recesses.In addition, potential difference corrosion occurs between the Ti and Al that aluminium film contains.

On the other hand, as known to from Figure 12 (b), it can not be seen and passed through using the surface of the aluminium base of sulphuric acid anodizing Potential difference corrodes formed recess.The oxide-film formed by using sulphuric acid anodizing is soft, due to being considered as by erosion Quarter is readily removable.As schematically, when using sulphuric acid anodizing, only relied on thereafter across 12 minutes in this as example The etching of progress, can remove anode oxide film.

Inquire into remove the necessary etching period of oxide-film formed by using sulphuric acid anodizing.Anodic oxidation Condition as with above-mentioned condition (fixed current 115A/m², 20 DEG C, 24 points 30 seconds) it is identical, use phosphate aqueous solution (concentration： 0.3mass%), with 30 DEG C, change it within 1 minute, 3 minutes, 5 minutes, 10 minutes and 12 minutes etching period, investigation oxidation The presence or absence of film remaining.As a result, being carried out more than 5 minutes by etching, oxide film dissolving can be removed by knowing.The example of experimental result In following presentation.

Figure 13 (a)~(d), be represent using sulfuric acid with after above-mentioned condition anodic oxidation by the phosphoric acid etch time not With sample surface SEM pictures (10000 times, the full size in SEM pictures is 200nm).Figure 13 (a) is 12 points of etching period Clock, Figure 13 (b) is etching period 10 minutes, and Figure 13 (c) is etching period 5 minutes, and Figure 13 (d) is the etching period examination of 3 minutes The SEM pictures of material.Beyond the etching period sample of 3 minutes (with reference to 13 (d)), oxide-film is removed.But, because at 5 minutes Etching is visually to confirm uneven situation, so etching period is preferably to be set in more than 10 minutes.

Inquire on do not apply cold-drawn processing, using by cutter grinding carry out mirror finish aluminium base (JIS A6063 the time that satin weave processing is carried out after the above-mentioned anodic oxidation and etching as preposition processing) is applied.Pass through preposition processing The presence or absence of because the state on the surface of aluminium base is different, it is advantageous to satin weave processing time be recognized as it is different can Can property.

After being carried out such as above-mentioned anodic oxidation and etching, with the aqueous solution (concentration containing ammonium acid fluoride：4mass%, temperature Degree：20 DEG C), processing time carried out satin weave processing with 30 seconds, 60 seconds, 120 seconds.Using the mould base material of acquisition, sample is made thin Film, reference picture 8 (b) is in method same as described above, and the result for assessing light distribution property is represented in Figure 14.Figure 14 also with Fig. 8 (a) identical, signal sets incidence angle and takes acceptance angle as transverse axis as 5 °, and the maximum for the intensity that diffuses is standardized as 80% Take the common logarithm of relative diffusing reflection rate (%) as the light distribution curve of the longitudinal axis.

As from known to Figure 14, the time of satin weave processing is distributed for the light of the sample film of 30 seconds, narrower than REF_No.1 It is narrow, without sufficient anti-glare function.The time of satin weave processing is distributed for the light of the sample of 60 seconds and 120 seconds, with light The inclination of line distribution curve is that the point discontinuously changed is present in acceptance angle more than 0 ° in less than 10 ° of scope, and relatively Diffusing reflection rate (%) feature so in less than 10% scope more than 1%.

Therefore, do not apply cold-drawn in use to process, using the aluminium base making for carrying out mirror finish by cutter grinding Mould base material, apply as after the anodic oxidation and etching of above-mentioned preposition processing carry out satin weave processing time, using containing The aqueous solution (the concentration of ammonium acid fluoride：4mass%, temperature：20 DEG C) when, it may be said that it is preferably more than 60 seconds.

Figure 15 (a), is to represent that applying the aluminium base for carrying out mirror finish by cutter grinding after cold-drawn processing is carried out 37 seconds The SEM pictures on the surface of the satin weave processing of (reference picture 10A), are to represent not apply with the aluminium base that duct method makes in Figure 15 (b) Cold-drawn is processed, and the aluminium base of mirror finish is being carried out by cutter grinding, the anodic oxidation and etching as preposition processing is carried out Afterwards, the SEM pictures on the surface of (reference picture 14) satin weave processing in 120 seconds are carried out.Any SEM pictures are all 10000 times, complete in SEM pictures Yardstick is 5 μm.

As from known to Figure 15 (a) and (b), from handled by satin weave the grand convex portion to be formed (reference picture 1 (c) it is grand convex Portion 18p) two-dimensional (area equivalent circle diameter) of normal to a surface direction when see, be all more than about 1 μm and 5 μm Below.The two-dimensional of grand convex portion is averaged, compared with grand recess it is average it is adjacent between distance (AD_int, reference picture 1 (b)) and it is smaller.

The ophthalmically acceptable mould of moth is made in the same manner as described above using these aluminium bases, reference picture 5 is same as described above, make sample thin Film.Obtain the antireflection film for having anti-glare function, liquid crystal display panel (diagonal 4.97 inches, point spacing is (in Figure 16 Px) for 19.1 μm, about 57.3 μm of pel spacing, about 440ppi) be attached at the surface of observer side, be known to visually evaluate When, suppress the strong light of display surface, and suppress the fuzzy of image.

[process for etching the surface of aluminium base]

Illustrate the preposition processing on being handled as satin weave, using alkaline etching liquid, the surface etching work procedure of aluminium base (is also had Be referred to as the situation of substrate surface etching work procedure) discussion result.

Apply satin weave processing in the aluminium base that mirror finish is carried out with cutter grinding, have to be formed on the surface of aluminium base and grind The situation of sheeter lines mark, this grinding vestige is considered as the surface due to the mirror finish aluminium base by being carried out with cutter grinding The etching for the affected layer being formed it is uneven.In addition, the antireflection film of the mould formation with grinding vestige will be used When being affixed on liquid crystal display panel, the situation for producing not train wave line is had.The generation of this not train wave line, it is considered to be because in The band of the grinding vestige of antireflection film transfer, with the point spacing (Px in Figure 16) of liquid crystal display panel or with pel spacing The periodic structure (such as pixel column) of arrangement is interfered with each other and caused.

A variety of discussion result, it is known that before the aqueous solution satin weave processing containing hydrogen fluoride and the salt of ammonia, by making With alkaline etching liquid, the surface of aluminium base is etched, grinding vestige can be lowered.

As shown in table 2 as described below, before satin weave processing, the substrate surface etching work procedure of condition change is carried out. Experimental example 1~7, is that the aluminium base (JIS A6063) for carrying out mirror finish by cutter grinding after cold-drawn processing using applying is made The mould base material of work is to carry out.

[table 2]

Alkaline etching solution E1 used, is organic basic remover (the limited public affairs of Yokohama oil prodution industry share in experimental example 1 The LC-2 of department) concentration be 8mass% the aqueous solution.The LC-2 of Yokohama oil prodution industry limited company, contains following group Into：2- ethylaminoethanols (12mass%), chelating agent (2mass%~6mass%), interfacial agent (2mass%~ 6mass%).Therefore, the concentration of the 2- ethylaminoethanols in alkaline etching solution E1 is 0.96mass%.The etching solution E1's of alkalescence PH value is 10.3.

The pH value of each alkaline etching solution, uses hand-held pH meter (ProductName：D-25, HORIBA Co., Ltd system) survey It is fixed.Lead to peralkaline etching solution and contain chelating agent, can prevent from etching cause dissolve the others contained in aluminium base Metal or impurity are attached to the surface of aluminium base.Because the etching solution of alkalescence contains interfacial agent, the etching of substrate surface by This is carried out with being able to uniformity.

Alkaline etching solution E3 used, is inorganic alkaline remover (the limited public affairs of Yokohama oil prodution industry share in experimental example 3 The L.G.L of department) concentration be 3mass% the aqueous solution.The L.G.L of Yokohama oil prodution industry limited company, containing following Composition：Potassium hydroxide (1mass%~3mass%), chelating agent (5mass%~15mass%), interfacial agent (5mass% ~15mass%).Therefore, the concentration of the potassium hydroxide in alkaline etching solution E3 is 0.03mass%~0.09mass%.Alkali Property etching solution E3 pH value be 11.7.

Alkaline etching solution E2 used in experimental example 2, is with the state placement 1 of ingress of air by the etching solution E3 of alkalescence More than individual month person.The etching solution E2 of alkalescence, alkalescence weak the etching solution E3 with than alkalescence.The etching solution E2 pH value of alkalescence is 9.92。

Among experimental example 1~3, sample is each impregnated in alkalescence etching solution (40 DEG C) fixed time after, pass through Sample is impregnated in pure water and washed.After washing, satin weave processing is not exclusively dryly carried out.In satin weave processing, using containing fluorine Change the aqueous solution (concentration of hydrogen ammonium：4mass%, temperature：10 DEG C), it is used as processing time within 5 minutes.

Among experimental example 4~6, handled after substrate surface etching work procedure without satin weave.Among experimental example 4~6, Using the alkaline etching solution E1~identical persons of E3 used in experimental example 1~3, substrate surface etching work procedure is carried out.

Alkaline etching solution E4 used, is inorganic alkaline remover (the limited public affairs of Yokohama oil prodution industry share in experimental example 7 The L.G.L of department) concentration be 0.10mass% the aqueous solution.Therefore, the concentration of the potassium hydroxide in alkaline etching solution E4 is 0.001mass%~0.003mass%.The etching solution E4 of alkalescence, is to use the etching solution E3 identical inorganic alkalines with alkalescence Remover modulation is formed, but its concentration is different.The etching solution E4 of alkalescence pH value is 10.38.Among experimental example 7, with experiment Example 1~3 is identical, and satin weave processing is carried out after substrate surface etching work procedure.

On experimental example 1~7, each carry out substrate surface etching work procedure and satin weave processing (or substrate surface etching work Sequence) aluminium base used as mould, formed anti-glare film.Anti-glare film, is to coat releasing agent (great Jin on the surface of aluminium base The Optool DSX of Industries, Inc) after, the ultraviolet hardening resin of acrylic acid series is coated, it is thin to be needed on TAC State irradiation ultraviolet radiation on film makes it harden and be formed.

The anti-glare film (sample film) obtained using aluminium base and from aluminium base, the assessment result of anti-glare function is represented In table 3.

[table 3]

Sample ID

Haze value

Ra(nm)

Not train wave line

It is uneven

Pattern

Anti-glare

Fade

Experimental example 1

10.21

95.93

○

Experimental example 2

22.87

202.2

○

Experimental example 3

28.16

243.2

○

△

Experimental example 4

9.99

78.51

○

×

○

Experimental example 5

4.87

41.49

○

×

○

Experimental example 6

21.84

352.76

○

×

○

Experimental example 7

-

×

-

Among table 3, " Ra ", " uneven " and " pattern " is the result for assessing aluminium base, " haze value ", " not train wave Line ", " anti-glare " and " colour fading ", are the results for assessing anti-glare film." haze value ", " Ra ", it is measurement result, " not train wave Line ", " uneven ", " pattern ", " anti-glare " are subjective evaluations by visual observation.Hereinafter, on respectively illustrating.

" Ra " of table 3, is the arithmetic average roughness Ra on the surface for representing aluminium base measurement result.Arithmetic mean roughness Ra is spent, is determined using Veeco Optical profiling system (Wyko NT1100).Lost by substrate surface Carve process and satin weave processing, the arithmetic average roughness Ra on the surface of aluminium base, be preferably for example more than 50nm and 300nm with Under.

" uneven " of table 3, is on producing whether uneven result to visually evaluate aluminium base surface.Assess aluminium base Whether the satin weave processing on material surface is carried out uniformity.On " uneven " of table 3, "○" is represented without uneven, "×" Indicate uneven.Among experimental example 7, because the alkali concentration that the alkaline etching liquid for substrate surface etching work procedure contains It is low, so being considered as fully removing affected layer.Illustrated by as after, the uneven situation (satin not produced Situation about carrying out line processing uniformity), for example remove about 1.4 μm from aluminium base surface.Among experimental example 7, with base material The thickness of the aluminium base of surface etching work procedure etching is small, causes satin weave processing not carry out uniformity, is considered as producing not Uniformly.

In addition, the reasons why as producing uneven among experimental example 7, following thing is contemplated.Experimental example 7 it The middle alkaline etching solution E4 used, is to use the alkaline etching solution E3 identical inorganic alkalines with being used among experimental example 3 Remover modulation is formed, but this low point of its concentration is different.Therefore, among experimental example 7, compared with experimental example 3, in the erosion of alkalescence Carve the alkali concentration that contains of liquid low, be considered as making aluminium base surface etching action weak.Among experimental example 7, in the etching of alkalescence The concentration for the chelating agent that liquid contains is similarly low, but because the other metals or the amount of impurity that contain in aluminium base, this A little ionic adsorption, chelating function, are compared the situation for also having less reduction with the situation of experimental example 3.Such as such situation, Because the function of chelating agent, it is considered as leading to the uneven consistent possible increasing of the etching on the surface of the aluminium base of peralkaline etching solution Greatly.This is the relation of the increase of the uneven uniformity of satin weave processing, is also considered as producing as a result uneven.

The alkali concentration that the etching solution of alkalescence contains, is preferably for example in more than 0.01mass%.The etching solution of alkalescence contains The inorganic alkali concentration having, is preferably for example in more than 0.03mass%.Organic alkali concentration that the etching solution of alkalescence contains, it is excellent Elect as example in more than 0.96mass%.

" pattern " of table 3, is to visually evaluate the result whether being formed in aluminium base picture on surface.Here, pattern is Refer to, such as anti-glare structure from hundreds times to thousands of times size concaveconvex shape.On " pattern " of table 3, "○" is represented There is no pattern generation, "×" to indicate pattern generation.On the aluminium base surface of experimental example 6, the concave-convex of about 1mm grades is generated Shape.By the pattern (concaveconvex shape) on this aluminium base surface, when anti-glare film is attached at into the surface of black acrylic plate, Also pattern is seen boldly.This pattern, because bigger from hundreds times to thousands of times than anti-glare construction, does not have anti-glare work( Energy.

The pattern (concaveconvex shape) on the surface of this aluminium base is considered as, such as the alkaline etching solution used in experimental example 6 E3 pH is 11.7, and therefore alkalescence is strong to produce.It is considered as making its necessity on aluminium base surface by the alkali of strong basicity with Shangdi It is coarse, produce pattern.Among substrate surface etching work procedure, alkaline etching solution also has the possibility for producing concentration gradient, may It is considered as one of the reason for pattern occurs.In addition, the pattern on aluminium base surface, for example, being recognized as being due to lead to Cross the mirror finish of cutter grinding progress, the affected layer that the surface of aluminium base is formed.Affected layer is not limited to, for example When aluminium base has the uneven uniformity of composition, it may be considered as one of the reason for generation as pattern.

On the aluminium base surface of experimental example 3, pattern is not produced.It is considered as the use by substrate surface etching work procedure The satin weave processing of the aqueous solution containing ammonium acid fluoride, the affected layer on aluminium base surface is partially removed, and/or, aluminium base The pattern on material surface becomes unobtrusively.

" haze value " of table 3, represents the measurement result of the haze value of anti-glare film.Haze value, uses Japanese electric color industry The mist degree instrument NDH2000 of limited company, is tried to achieve from (diffusing transmission rate/total light transmittance) × 100.

" the not train wave line " of table 3, LCD TV (AQUOS UD1, Sharp KK are attached at by anti-glare film System) display pannel surface, to visually evaluate the result that whether train wave line does not occur.On " the not train wave line " of table 3, " Zero " represents that train wave line, "×" do not indicate to produce not train wave line without generation.

" anti-glare " of table 3, by being attached at the anti-of black acrylic plate surface daylight lamp visually to observe anti-glare film Penetrate, judge the result that anti-glare whether there is.On " anti-glare " of table 3, "○" is to represent that judgement has anti-glare, "×" to be to represent to sentence Break no anti-glare.In general, the big anti-glare film of haze value, excellent in anti-glare function, it is excellent in anti-glare.

" colour fading " of table 3, LCD TV (AQUOS UD1, Sharp KK's system) is attached at by anti-glare film The surface of display pannel, on the picture through film, if take notice of the result faded and listened to.Listened to, closed for 5 people In " colour fading " of table 3, "○" represents that the number for answering " taking notice of to colour fading " is 0 people in 5 people, and " △ " represents to answer " to fading Take notice of " it is that more than 1 people and below 3 people, "×" represents it is more than 4 people.In general, the big anti-glare film of haze value, because its Anti-glare function, it is readily seen that being faded through the picture of film.

In addition, among above-mentioned, the assessment of " anti-glare " and " colour fading ", it is considered to be because evaluator wants the anti-glare realized The degree of function is different.For example, the assessment of above-mentioned table 3, haze value is appropriate anti-glare function in about more than 7 and about less than 24 Situation.By the mould manufactured by the mould manufacturing method of embodiment of the present invention, signal person as an example is not limited to, to shape Antireflection film into anti-glare function higher (having bigger haze value (e.g., from about more than 7 and about less than 28)) can also make With.To formed anti-glare function it is lower have smaller haze value (e.g., from about more than 1 and about less than 5)) antireflection film work as It can also so use.

Among substrate surface etching work procedure, about 1.4 μm are for example removed from the surface of aluminium base.With substrate surface etching work procedure The thickness of etching, such as by adjusting etching period, the temperature of etching solution, can suitably be adjusted.Etched with substrate surface The preferred thickness of process etching is different because of the state on the surface of such as aluminium base.Etched thickness is not limited to above-mentioned example, excellent Elect the degree that the affected layer on aluminium base surface is fully removed as, be etched.

From above-mentioned experimental example, in order to obtain have appropriate anti-glare function (for example haze value about more than 7 and about 24 with Under)) antireflection film, the alkaline etching solution pH used in substrate surface etching work procedure, be preferably such as more than 10 and 12 with Under.Situations of the pH of the etching solution of alkalescence below 9, the affected layer on aluminium base surface has the possibility that can not fully remove Property.Situations of the pH of the etching solution of alkalescence more than 13, aluminium base surface is necessary coarse with Shangdi, and/or has acquisition uneven The reason for possibility.

But, the pH for the alkaline etching solution that substrate surface etching work procedure is used preferred scope is because aluminium base Surface state is different and obtains.The surface state of aluminium base, for example, the species of aluminium base, preparation method, and/or because processing Method is different and obtains.

[being handled by the satin weave of alkaline etching liquid]

Illustrate, by the aqueous solution of salt of the satin weave processing substitution containing hydrogen fluoride and ammonia, to lead to the discussion knot that peralkaline etching solution is carried out Really.

Replace the aqueous solution of the salt containing hydrogen fluoride and ammonia, when leading to peralkaline etching solution progress satin weave processing, obtain Cicada is possible to lower grinding vestige.Lead to peralkaline etching solution, the etching on aluminium base surface simultaneously carried out with satin weave processing, It is considered as thus removing the affected layer formed on aluminium base surface.

As shown in table 4 below, the etching solution for changing alkalescence by condition carries out satin weave processing.Experimental example 8~15, with the heart The aluminium base that method of principal axes makes does not apply cold-drawn processing, uses the aluminium base (JIS that mirror finish is carried out by cutter grinding A6063) the mould base material made is used for carrying out.

[table 4]

Among experimental example 8,9 and 11, in alkalescence etching solution E1 (identical with user in above-mentioned experimental example 1) with will examination Material dipping has been fixed time, and carries out satin weave processing.

Among experimental example 10, in alkalescence etching solution E2 (identical with user in above-mentioned experimental example 2) so that sample to be soaked Stain has been fixed time, and carries out satin weave processing.

The alkaline etching solution E5 used in experimental example 12, is to place the etching solution E1 of alkalescence with the state of ingress of air More than 1 month person.The etching solution E5 of alkalescence, alkalescence weak the etching solution E1 with than alkalescence.The etching solution E5 pH of alkalescence is 9.20。

Among experimental example 13 and 14, in alkalescence etching solution E3 (identical with user in above-mentioned experimental example 3) with will examination Material dipping has been fixed time, and carries out satin weave processing.

Among experimental example 15, in alkalescence etching solution E4 (identical with user in above-mentioned experimental example 7) so that sample to be soaked Stain has been fixed time, and carries out satin weave processing.

Among experimental example 8~15, sample is each impregnated into thickness of having fixed time in alkaline etching solution (40 DEG C), by inciting somebody to action Sample is impregnated in pure water and washed.After washing, sample is dried.

On experimental example 8~15, the aluminium base for carrying out satin weave processing each via the etching solution of alkalescence is used as mould, Form anti-glare film.Anti-glare film, is that the mould release (Optool of Daikin Industries, Ltd. is coated on the surface of aluminium base DSX after), the ultraviolet hardening resin of acrylic acid series is coated, makes its hard in the state irradiation ultraviolet radiation in PET film with transcription Change, and formed.

The anti-glare film (sample film) obtained using aluminium base and from aluminium base, the assessment result of anti-glare function is represented In table 5.Symbol in appraisal procedure and table 5 is identical with the explanation on above-mentioned table 3.

[table 5]

Sample ID

Haze value

Ra(nm)

Not train wave line

It is uneven

Pattern

Anti-glare

Fade

Experimental example 8

18

121.02

○

Experimental example 9

16.36

51.98

○

Experimental example 10

9.2

62.76

○

Experimental example 11

13

47.27

×

○

Experimental example 12

-

×

-

Experimental example 13

3.3

-

×

○

×

○

Experimental example 14

19.59

210.75

○

×

○

×

Experimental example 15

-

×

-

Among experimental example 11, occurs not train wave line.Compared with without occurring the not experimental example 8 and experimental example 9 of train wave line, It is among experimental example 11, sample is short in the time of the etching solution E1 dippings of alkalescence.Among experimental example 11, the not production of train wave line Life is considered as that the etching of the affected layer on the surface due to aluminium base is insufficient.

Among experimental example 12 and experimental example 15, produce uneven.Among experimental example 12, the alkaline etching solution used E5 pH value is 9.20, because alkalescence is weak, is considered as fully removing affected layer.Among experimental example 15, because The alkali concentration contained for the etching solution E4 of alkalescence is low, so being considered as fully removing affected layer.Such as it It is illustrated afterwards, the uneven situation (situation about carrying out) not produced satin weave processing uniformity, from the surface of aluminium base for example Remove about 1.4 μm.Among experimental example 12 and experimental example 15, the thickness of the aluminium base etched with substrate surface etching work procedure is small, Cause satin weave processing not carry out, it is considered to be uneven generation uniformity.

In addition, the reasons why among experimental example 15 as producing uneven, as on above-mentioned experimental example 7, it is considered to be Caused by the function of chelating agent.In following explanation.

The alkaline etching solution E4 used among experimental example 15, the alkali concentration that alkaline etching solution contains is low.In reality The pH value for testing the alkaline etching solution E5 used among example 12 is 9.20, and alkalescence is weak.Therefore, experimental example 12 and experimental example 15 it In, it is considered as making the surface etching action of aluminium base weak.But, among experimental example 12 and experimental example 15, because in aluminium base The other metals or the amount of impurity contained, these ionic adsorption, chelating function is considered as also having less low situation.So Situation because the function of chelating agent, be considered as lead to peralkaline etching solution aluminium base surface etching uneven one Cause may increase.This is the relation of the increase of the uneven uniformity of satin weave processing, is also considered as producing inequality as a result It is even.

The alkali concentration that the etching solution of alkalescence contains, is preferably such as more than 0.01mass%.The etching solution of alkalescence contains Inorganic alkali or organic alkali concentration, be preferably such as more than 0.03mass%.The organic salt that the etching solution of alkalescence contains The concentration of base, is preferably such as more than 0.96mass%.

Among experimental example 13 and experimental example 14, pattern is produced.Among experimental example 13 and experimental example 14, because use The etching solution E3 of alkalescence pH is higher, so being considered as making the surface of aluminium base necessary thick with Shangdi by the alkali of strong basicity It is rough.Thus, it is considered as generating pattern.In addition, as on above-mentioned table 3, the pattern that the surface of aluminium base is produced, for example, It is considered as the affected layer that the surface of aluminium base is formed due to the mirror finish carried out by cutter grinding.

From above-mentioned experimental example, because the arithmetic average on the surface of the aluminium base of logical peralkaline etching solution satin weave processing is thick Rugosity Ra, is preferably such as more than 50nm and below 200nm.

Lead among peralkaline etching solution satin weave treatment process, about 1.4 μm are for example removed from the surface of aluminium base.Etching Thickness, by adjusting such as etching period, the temperature of etching solution etc., can suitably be adjusted.The preferred thickness of etching, because for example The state on the surface of aluminium base and it is different.Etched thickness is not limited to the affected layer of above-mentioned example, preferably aluminium base surface The degree fully removed, is etched.

Lead to peralkaline etching solution satin weave treatment process, by the surface of aluminium base, in the etching solution of alkalescence, for example, by 45 Contact to carry out more than point.Thus, lead to peralkaline etching solution satin weave treatment process, can double as being degreasing process.

By above-mentioned experimental example, in order to obtain the anti-glare function with appropriateness, (such as haze value is about more than 7 and about Less than 24) antireflection film, for the pH value of the alkaline etching liquid of satin weave processing, is known preferably such as more than 9.5 and 11 Below.Situation of the pH value of the etching solution of alkalescence below 9, what the affected layer for having aluminium base surface can not be removed fully Possibility.Situation of the pH value of the etching solution of alkalescence more than 13, aluminium base surface is necessary coarse with Shangdi, and/or has satin weave Handle the possibility that can not be carried out uniformity.

But, the pH of the alkaline etching solution used in satin weave processing preferred scope is the surface shape because aluminium base State is different and obtains.The surface state of aluminium base, for example, the species of aluminium base, preparation method, and/or because of processing method not Obtain together.

In addition, by the mould manufactured by the mould manufacturing method of embodiment of the present invention, being not limited to illustrate as an example Person, the antireflection film to form anti-glare function higher (there is bigger haze value (e.g., from about more than 7 and about less than 28)) It can also use.To be formed, anti-glare function is lower to have smaller haze value (e.g., from about more than 1 and about less than 5)) it is anti- Reflectance coating can certainly be used.

Using the cylindric aluminium base that satin weave is handled that is applied with of such gained, as above-mentioned, by by reversion moth eye The formation of structure, anti-reflective function and the ophthalmically acceptable mould of moth of anti-glare function can be assigned by obtaining.Moth using cylindrical shape is ophthalmically acceptable When mould, so that antireflection film can be formed such as above-mentioned roll-to-roll mode.Now, antireflection film is formed to be lifted Adaptation of the film substrate (TAC film or PET film) between antireflection film, preferably by such as following process.

On TAC film, uv-hardening resin (such as propylene of (such as 2 μm~20 μm of thickness) containing solvent is assigned Acid system resin).Now, solvent is selected the surface dissolving person (such as ketone system) of TAC film.By solvent by the table of TAC film Face is dissolved, and forms the region that TAC is mixed with uv-hardening resin.

Thereafter, solvent is removed, in the outer peripheral face of the ophthalmically acceptable mould of moth, TAC film is rolled up, so that uv-hardening resin It is closely sealed.

Then, irradiation ultraviolet radiation, hardens uv-hardening resin.Now, the temperature of uv-hardening resin is protected Hold from 30 DEG C to 70 DEG C.

Thereafter, TAC film is peeled off from the ophthalmically acceptable mould of moth, if it is necessary, irradiation ultraviolet radiation once again.

It is the situation that hard conating is formed on TAC film, is forming the material of hard conating, can also contain TAC film The solvent of surface dissolving.This situation, it is not necessary to contain solvent in the uv-hardening resin to form antireflection film.

In addition, using the situation of PET film, before uv-hardening resin is assigned, preferably forming aqueous bottom Paint the layer (2 μm~20 μm of thickness) of (for example, polyester fiber resin or acrylic resin).This situation, it is not necessary to shape Uv-hardening resin into antireflection film contains solvent.

The manufacture method of inventive die, is used in the mould for being suitably used for forming antireflection film (reflectance coating) surface etc. Tool manufacture.The antireflection film of the present invention, the anti-glare function with performance appropriateness, the surface knot with excellent anti-reflective function Structure, for example, being suitably used for the display panel of fine.

The explanation of reference

10 mould base materials

12 aluminium bases

14 porous alumina layers

14p nicks portion

16 inorganic material layers

18 aluminium films

18r aluminium rest layers

The ophthalmically acceptable mould of 100 moths

Claims

1. a kind of manufacture method of mould, comprising：

(a) work of aluminium base that cylindrical shape is formed with the aluminium alloy of Al-Mg-Si systems and mechanicalness mirror finish is applied in is prepared Sequence；

(b) surface of the aluminium base is led to the process of peralkaline etching solution satin weave processing；

(c) after the process (b), by forming inorganic material layer on the surface of the aluminium base, described inorganic Process of the aluminium film to make mould base material is formed on material layer；

(d) after the process (c), by making the surface anodization of the aluminium film, form many with multiple nick portions The process of porous aluminum oxide layer；

(e) after the process (d), by making the porous alumina layer contact etching solution, the Woelm Alumina is expanded The process in the multiple nick portion of layer；And

(f) after the process (e), by further anodic oxidation, the process of the multiple nick portion growth is made.

2. the manufacture method of mould as claimed in claim 1, it is characterised in that by the process (b), the aluminium base The arithmetic average roughness Ra on the surface is more than 50nm and below 200nm.

3. the manufacture method of mould as claimed in claim 1 or 2, it is characterised in that the alkaline etching solution contains More than 0.03mass% inorganic alkali or organic alkali.

4. the manufacture method of mould as claimed any one in claims 1 to 3, it is characterised in that the alkaline etching solution PH value be more than 9.5 and less than 11.

5. the manufacture method of the mould as any one of Claims 1-4, it is characterised in that the alkaline etching solution Contain the organic compound with amido.

6. the manufacture method of the mould as any one of claim 1 to 5, it is characterised in that the alkaline etching solution Contain potassium hydroxide.

7. the manufacture method of the mould as any one of claim 1 to 6, it is characterised in that in the process (b), from The surface of the aluminium base removes at least 1.4 μm.

8. the manufacture method of the mould as any one of claim 1 to 7, it is characterised in that the process (b) is to pass through Make the surface of the aluminium base contact the alkaline etching solution to carry out for more than 45 minutes.

9. the manufacture method of the mould as any one of claim 1 to 8, it is characterised in that the process (b) is as de- Fat process.

10. the manufacture method of mould as claimed in any one of claims 1-9 wherein, it is characterised in that the aluminium base is to pass through The aluminium base of heart method of principal axes formation.

11. a kind of mould, by manufactured by the manufacture method of the mould any one of claim 1 to 10.

12. a kind of mould, with the porous alumina layer for possessing surface structure；

There is the surface structure two-dimensional when in terms of normal to a surface direction to be less than more than 200nm and 30 μm Multiple grand convex portions and two-dimensional when in terms of normal to a surface direction are for more than 10nm and less than the multiple micro- of 500nm Recess.

13. a kind of manufacture method of antireflection film, comprising：

Prepare the process of the mould described in claim 11 or 12；

Prepare the process of machined object；

Between the surface of the mould and the machined object in the state of imparting light-hardening resin, by the photo-hardening Resin irradiation light is so that the process of light-hardening resin hardening；And

The process that the mould is peeled off from the antireflection film of the light-hardening resin formation with hardening.

14. a kind of antireflection film, by manufactured by the manufacture method of the antireflection film described in claim 13.

15. antireflection film as claimed in claim 14, it is characterised in that haze value is about more than 7 and about less than 24.